CN115246853A - Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, or lighting device - Google Patents

Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, or lighting device Download PDF

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CN115246853A
CN115246853A CN202210442993.2A CN202210442993A CN115246853A CN 115246853 A CN115246853 A CN 115246853A CN 202210442993 A CN202210442993 A CN 202210442993A CN 115246853 A CN115246853 A CN 115246853A
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畠山琢次
田中裕之
前田健永
井上大辅
諌山康平
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Kwansei Gakuin Educational Foundation
SK Materials JNC Co Ltd
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Abstract

The invention provides a polycyclic aromatic compound which is effectively used as an organic device material such as an organic EL element, a material for an organic device, an organic electroluminescent element, a display device or a lighting device. A polycyclic aromatic compound having one or more structures containing a structural unit represented by formula (1); z is N or C-R 11 (R 11 Is hydrogen or a substituent), and the C ring is of the formula (C) Ring represented by, Z C Is N or C-R C (R C Is hydrogen or a substituent), X c Is > S, etc., Y 1 Is B, X 1 And X 2 One is > N-GA, the other is > N-GB, GA and GB are monovalent radicals represented by formula (GA) and formula (GB), respectively, and are bonded with N at any position, Z a Is N or C-R a ，Z b Is N or C-R b (R a 、R b Is hydrogen or a substituent), a is > O, etc., an aryl or heteroaryl ring in said structure may be condensed with a cycloalkane, at least one hydrogen in said structure may be substituted with cyano, halogen or deuterium.
Figure DDA0003615335210000011

Description

Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, or lighting device
Technical Field
The present invention relates to a polycyclic aromatic compound. The invention relates in particular to a polycyclic aromatic compound containing nitrogen and boron. The present invention also relates to a material for an organic device, an organic electroluminescent element, a display device, and a lighting device, each containing the polycyclic aromatic compound.
Background
Conventionally, various studies have been made on display devices using light emitting elements that perform electroluminescence, because they can achieve power saving and reduction in thickness, and further, active studies have been made on organic electroluminescence elements including organic materials, because they are easy to reduce the weight and increase the size. In particular, active studies have been made on the development of an organic material having light-emitting characteristics such as blue, which is one of the three primary colors of light, and an organic material having charge transport capability (having a possibility of becoming a semiconductor or a superconductor) of holes, electrons, and the like, both of a high-molecular compound and a low-molecular compound.
The organic electroluminescent element has a structure including: a pair of electrodes including an anode and a cathode, and one or more layers which are disposed between the pair of electrodes and include an organic compound. The layer containing an organic compound includes a light-emitting layer, a charge transporting/injecting layer for transporting or injecting charges such as holes and electrons, and various organic materials suitable for the layers have been developed.
Among them, patent documents 1 to 5 disclose that polycyclic aromatic compounds containing boron are effectively used as materials for organic electroluminescent elements and the like. And it has been reported that the organic electroluminescent element containing the polycyclic aromatic compound has good external quantum efficiency. Patent documents 2 and 3 disclose a structure obtained by condensation of a heterocycle such as benzothiophene. Patent document 4 discloses a structure in which a heterocycle such as a dibenzofuran ring is introduced into a substituent moiety. Patent document 5 discloses a structure in which biphenyl is introduced.
[ Prior art documents ]
[ patent document ]
[ patent document 1] International publication No. 2015/102118
[ patent document 2] International publication No. 2020/111830
[ patent document 3] International publication No. 2020/251049
[ patent document 4] International publication No. 2019/132028
[ patent document 5] International publication No. 2019/102936
Disclosure of Invention
[ problems to be solved by the invention ]
As described above, various materials have been developed as materials for organic Electroluminescence (EL) devices, but in order to increase the options of materials for organic EL devices, it is desired to develop materials containing compounds different from those in the past.
The present invention addresses the problem of providing a novel compound which is useful as a material for organic devices such as organic EL elements.
[ means for solving problems ]
The present inventors have made extensive studies to solve the above problems, and have succeeded in producing a polycyclic aromatic compound having high luminous efficiency and the like by combining a specific condensed ring structure with a substituent in the structures of the compounds described in patent documents 1 to 5. Further, the present inventors have found that an excellent organic EL element can be obtained by disposing a layer containing the polycyclic aromatic compound between a pair of electrodes to form an organic EL element, and have completed the present invention. That is, the present invention provides a polycyclic aromatic compound as described below, and a material for an organic device and the like containing the polycyclic aromatic compound as described below.
The present invention specifically has the following configuration.
[1] A polycyclic aromatic compound having one or more structures containing a structural unit represented by the following formula (1);
[ solution 1]
Figure BDA0003615335190000021
In the formula (1), the reaction mixture is,
z is each independently N or C-R 11 Wherein Z = Z can be > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
R 11 each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylA boron group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silane group,
the two aryl groups of the diarylamino group are not bonded to each other or are bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group are not bonded to each other or are bonded via a linking group, the aryl group and the heteroaryl group of the arylheteroarylamino group are not bonded to each other or are bonded via a linking group, the two aryl groups of the diarylboron group are not bonded to each other or are bonded via a single bond or a linking group,
two adjacent R 11 Are bonded to each other to form an aryl or heteroaryl ring, or are not bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of the formed aryl and heteroaryl rings being independently of each other via R 11 Substituted or unsubstituted, C ring is a ring represented by formula (C),
in the formula (C), X c Is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
Z C each independently is N or C-R C ，
R C Each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkeneA group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group, the two aryl groups of the diarylamino group being not bonded to each other or to each other via a linking group, the two heteroaryl groups of the diheteroarylamino group being not bonded to each other or to each other via a linking group, the aryl group and heteroaryl group of the arylheteroarylamino group being not bonded to each other or to each other via a linking group, the two aryl groups of the diarylboron group being not bonded to each other or to each other via a single bond or a linking group,
two adjacent R C Can be bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of said aryl and heteroaryl rings being independently of each other via R C Either substituted, or unsubstituted,
wherein any two consecutive Z C In which one is with Y 1 The bound carbon, another being with X 2 A bonded carbon;
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 One is > N-GA, the other is > N-GB,
GA is a monovalent group represented by the formula (GA);
in the formula (GA), the compound is represented by the formula (GA),
Z a are each independently N or C-R a ，
R a Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted heteroaryl boronAryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl radicals of the diarylamino radical not being bonded to one another or via a linking group, the two heteroaryl radicals of the diheteroarylamino radical not being bonded to one another or via a linking group, the aryl and heteroaryl radicals of the arylheteroarylamino radical not being bonded to one another or via a linking group, the two aryl radicals of the diarylboron radical not being bonded to one another or via a single bond or a linking group,
two adjacent R a May be bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of which is represented by R a Either substituted, or unsubstituted,
a is > O, > N-R, > Si (-R) 2 、＞C(-R) 2 R > N-R, said > Si (-R) 2 R of (b), and said > C (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > Si (-R) 2 Two R of (a) and said > C (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
wherein the monovalent group represented by the formula (GA) is bonded to X at any position 1 Or X 2 N-GA in the group (b);
GB is a monovalent radical represented by the formula (GB),
in the formula (GB), the reaction mixture is,
Z b are each independently N or C-R b ，
R b Each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxyA substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group, the two aryl groups of the diarylamino group being not bonded to each other or via a linking group, the two heteroaryl groups of the diheteroarylamino group being not bonded to each other or via a linking group, the aryl and heteroaryl groups of the arylheteroarylamino group being not bonded to each other or via a linking group, the two aryl groups of the diarylboron group being not bonded to each other or via a single bond or a linking group,
two adjacent R b Can be bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of said aryl and heteroaryl rings being independently of each other via R b Either substituted, or unsubstituted,
wherein the monovalent group represented by the formula (GB) is bonded to X at any position 1 Or X 2 N-GB;
at least one of the structures selected from the group consisting of aryl and heteroaryl rings is condensed or not condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane being substituted, at least one-CH in the cycloalkane 2 -is substituted by-O-, or unsubstituted, and;
at least one hydrogen in the structure is substituted with cyano, halogen, or deuterium, or unsubstituted.
[2] The polycyclic aromatic compound according to [1], wherein the structural unit represented by the formula (1) is represented by the formula (1 a), the formula (1 b), the formula (1 c), the formula (1 d), the formula (1 e), the formula (1 f), the formula (1 g) or the formula (1 h);
[ solution 2]
Figure BDA0003615335190000051
[ solution 3]
Figure BDA0003615335190000052
In the formula (1 a), the formula (1 b), the formula (1 c), the formula (1 d), the formula (1 e), the formula (1 f), the formula (1 g) and the formula (1 h),
z is each independently N or C-R 11 Wherein Z = Z may each independently be > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
R 11 each independently of the others being hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl groups of the diarylamino group not being bonded to each other or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group not being bonded to each other or being bonded via a linking group, the aryl group of the arylheteroarylamino group not being bonded to a heteroaryl group or being bonded via a linking group, the two aryl groups of the diarylboron group not being bonded to each other or being bonded via a single bond or a linking group,
two adjacent R 11 Are bonded to each other to form an aryl or heteroaryl ring, or are not bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of the formed aryl and heteroaryl rings being independently of each other via R 11 Substituted, or unsubstituted;
X c is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
Z C each independently is N or C-R C ，R C Each independently of the other is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl radicals of the diarylamino radical being not bonded to one another or being bonded via a linking group, the two heteroaryl radicals of the diarylamino radical being not bonded to one another or being bonded via a linking group, the aryl and heteroaryl radicals of the arylheteroarylamino radical being not bonded to one another or being bonded via a linking group, the two aryl radicals of the diarylboron radical being not bonded to one another or being bonded via a single bond or a linking group,
two adjacent R C Can be bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of said aryl and heteroaryl rings being independently of each other via R C Substituted, or unsubstituted;
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 One is > N-GA, the other is > N-GB,
GA is a monovalent group represented by the formula (GA);
GB is a monovalent group represented by the formula (GB);
at least one of the structures selected from the group consisting of aryl and heteroaryl rings is condensed or not condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane being substituted, at least one-CH in the cycloalkane 2 -O-substituted, or unsubstituted, and;
at least one hydrogen in the structure is substituted with cyano, halogen, or deuterium, or unsubstituted.
[3] The polycyclic aromatic compound according to [2], wherein the structural unit represented by the formula (1) is represented by the formula (1 a).
[4]According to [1]]To [3]]The polycyclic aromatic compound of any one of the above, wherein Z is all C-R 11 。
[5] The polycyclic aromatic compound according to any one of [1] to [4], wherein the monovalent group represented by the formula (GA) is a group represented by the formula (GA-1) or the formula (GA-4) wherein the group having a substituent is one of the groups represented by the formula (GA-1) or the formula (GA-4) wherein one or two of the hydrogen atoms of the group represented by the formula (GA-1) or the formula (GA-4) are substituted with an alkyl group or a cycloalkyl group, and
the monovalent group represented by the formula (GB) is a group represented by the formula (GB-1), the formula (GB-3), the formula (GB-6), the formula (GB-13) or the formula (GB-14) wherein R is a substituent, a group represented by the formula (GB-1), the formula (GB-3), the formula (GB-6), the formula (GB-13) or the formula (GB-14) wherein one or two hydrogens of the group represented by R is a substituent are substituted with an alkyl group or a cycloalkyl group, or a group represented by the formula (GB-1), the formula (GB-3), the formula (GB-6), the formula (GB-13) or the formula (GB-14) wherein at least one of the benzene rings of the group represented by the formula (GB-1), the formula (GB-3), the formula (GB-6), the formula (GB-13) or the formula (GB-14) wherein R is a substituent is a cycloalkane wherein R is a substituent.
[ solution 4]
Figure BDA0003615335190000071
[6] The polycyclic aromatic compound according to [1], which is represented by any one of the following formulae;
[ solution 5]
Figure BDA0003615335190000072
[ solution 6]
Figure BDA0003615335190000081
[ solution 7]
Figure BDA0003615335190000091
[ solution 8]
Figure BDA0003615335190000101
In the formula, me is methyl, tBu is tert-butyl, and D is deuterium.
[7] A material for organic devices, comprising the polycyclic aromatic compound according to any one of [1] to [6 ].
[8] An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer disposed between the pair of electrodes, the light-emitting layer containing the polycyclic aromatic compound according to any one of [1] to [6 ].
[9] The organic electroluminescent element according to [8], wherein the light-emitting layer comprises a host, and the polycyclic aromatic compound as a dopant.
[10]According to [9]]The organic electroluminescent element described in the above, wherein the host is an anthracene compound, a fluorene compound, or a dibenzo
Figure BDA0003615335190000111
A compound is provided.
[11] A display device or a lighting device comprising the organic electroluminescent element according to any one of [8] to [10 ].
[ Effect of the invention ]
According to the present invention, a novel polycyclic aromatic compound which is effectively used as a material for an organic device such as an organic electroluminescent element can be provided. The polycyclic aromatic compound of the present invention can be used for producing an organic device such as an organic electroluminescent device.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of an organic electroluminescent element.
Fig. 2 is an energy level diagram showing the energy relationship among the host, the assist dopant, and the emissive dopant of a TAF element using a general fluorescent dopant.
Fig. 3 is a level diagram showing an example of an energy relationship among a host, an auxiliary dopant, and an emitting dopant in an organic electroluminescent device according to an embodiment of the present invention.
[ description of symbols ]
100: organic electroluminescent element
101: substrate
102: anode
103: hole injection layer
104: hole transport layer
105: luminescent layer
106: electron transport layer
107: electron injection layer
108: cathode electrode
Detailed Description
The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments or specific examples, but the present invention is not limited to such embodiments. In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the lower limit value and the upper limit value. In addition, "hydrogen" in the description of the structural formulae in the present specification means "hydrogen atom (H)". In this specification, an organic electroluminescent element is sometimes referred to as an organic EL element.
In the present specification, the chemical structure or the substituent is sometimes represented by a carbon number, but the carbon number when the substituent is substituted in the chemical structure or when the substituent is further substituted on the substituent means the carbon number of each of the chemical structure or the substituent, and does not mean the total carbon number of the chemical structure and the substituent or the total carbon number of the substituent and the substituent. For example, the "substituent B having a carbon number Y substituted with the substituent a having a carbon number X" means that the "substituent a having a carbon number X" is substituted with the "substituent B having a carbon number Y, and the carbon number Y is not the total carbon number of the substituent a and the substituent B. For example, the "substituent B having a carbon number Y substituted by the substituent a" means that the substituent a "(not limited to a carbon number) is substituted on the" substituent B having a carbon number Y ", and the carbon number Y is not the total carbon number of the substituent a and the substituent B.
Since the chemical structural formula described in the present specification (including a general formula depicted by a markush (markush) structural formula as in formula (1) described later) is a planar structural formula, various isomeric structures such as an enantiomer (enantiomer), a diastereomer, or a rotamer may actually exist. In the present specification, unless otherwise specified, the compounds described may have any isomeric structure that can be considered from the plane structural formula thereof, and may be a mixture of possible isomers in any ratio.
The present specification describes structural formulae of a plurality of aromatic compounds. An aromatic compound is described by combining a double bond and a single bond, but actually, since pi-electron resonance occurs, there is an equivalent resonance structure in which a plurality of double bonds and single bonds are alternately replaced with each other for a single substance. In the present specification, only one resonance structural formula is described for one substance, but other resonance structural formulas that are equivalent in organic chemistry are also included unless otherwise specified. The above case is referred to in the description of "Z = Z" and the like described later. That is, for example, "Z = Z" in formula (1) described later is as follows as an example. However, the present invention is not limited to this, and it is needless to say that the present invention is applicable not only to one resonance structural formula described above but also to other equivalent resonance structural formulas.
[ solution 9]
Figure BDA0003615335190000121
In addition, the expression "capable of going" used in the present specification means "not going, or, both expressions have been described, but both expressions have the same meaning.
In the present specification, the expression "adjacent to" means that they are adjacent to each other on the same ring unless otherwise specified.
In the present specification, a substituent is sometimes further substituted with a substituent. (with respect to substituents, sometimes described as "substituted or unsubstituted"). This means that at least one hydrogen of a substituent ("first substituent" or "first substituent") is further substituted with a substituent ("second substituent" or "second substituent"), or unsubstituted. The first substituent (first substituent) and the second substituent (second substituent) may be referred to in the description, respectively.
< 1. Polycyclic aromatic Compound >
The polycyclic aromatic compound of the present invention is a polycyclic aromatic compound having one or more structures containing the structural unit represented by formula (1). The polycyclic aromatic compound of the present invention has a high luminescence quantum yield (PLQY), a narrow luminescence half-value width, and excellent color purity.
[ solution 10]
Figure BDA0003615335190000122
In the formula (1), Z in the ring A and the ring B is respectively and independently N or C-R 11 Or Z = Z is each independently > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring. Here, the aryl, heteroaryl, alkyl, and cycloalkyl groups are referred to as a first substituent. These groups are described as "substituted or unsubstituted", but in the case where at least one hydrogen is substituted, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, or substituted silane groups are preferred. These aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silane groups are referred to as a second substituent.
C-R 11 R of (A) to (B) 11 Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl. Here, the aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, arylthio, and substituted silyl groups are referred to as a first substituent. These groups are described as "substituted or unsubstituted", but in the case where at least one hydrogen is substituted, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, or substituted silane groups are preferred. These aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, and substituted silane groups are referred to as second substituents.
As R 11 Preferably, it is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, or substituted silyl.
Next, for "Z = Z, each is independently > O, > N-R, > C (-R) 2 、＞Si(-R) 2 (ii) S, or > Se ″)The description of the sample is explained. For example, in the A ring in formula (1), the site "Z = Z" is substituted with > O, > N-R, > C (-R) 2 、＞Si(-R) 2 Rings obtained by "S" or "Se" include: cyclopentadiene rings, pyrrole rings, furan rings, thiophene rings, and the like. Examples thereof include A ring and the like, wherein one Z = Z is > N-R, > O, > S, > C (-R) 2 And the remaining Z is C-R 11 And one Z = Z is > N-R, > O, > S, > C (-R) 2 And the remaining Z is C-R 11 R's adjacent to each other as described later 11 Examples of the formation of benzene rings. However, the form that the a ring and the like can take is not limited to the following examples.
[ solution 11]
Figure BDA0003615335190000141
As described above, since the aromatic compound has a resonance structure which is completely equivalent in organic chemistry, it can be based on any possible resonance structure. Further, the > N-R, the > C (-R) as Z = Z 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring. These groups are described as "substituted or unsubstituted", but where at least one hydrogen is substituted, preferably are aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, or substituted silyl groups. The aryl group of the diarylamino group is substituted with an alkyl group or a cycloalkyl group, or is unsubstituted. For the first substituent and the second substituent, and for statements and preferred ranges thereof used herein, reference may be made to the description in the specification.
In the formula (1), Z is preferably all C to R independently 11 . In this case, it is also preferable that Y is formed on the benzene ring 1 R in para position of (2) 11 Is hydrogen or a substituent other than hydrogen, other R 11 Is hydrogen. In the B ring, Y is more preferably formed on the benzene ring 1 R in para position of (2) 11 Is a substituent other than hydrogen, other R 11 Is hydrogen. Examples of the substituent in this case include preferable substituents described later as the first substituent, and examples thereof include: a tertiary alkyl group (e.g., a tertiary butyl group or a tertiary pentyl group) represented by the formula (tR), a cycloalkyl group, a diarylamino group or an arylheteroarylamino group which may be substituted with the tertiary alkyl group or the alkyl group represented by the formula (tR), and the like. In the A ring, Y is more preferably formed on the benzene ring 1 R of para position 11 Is hydrogen or alkyl (methyl or tert-butyl, etc.), other R 11 Is hydrogen.
Two adjacent R 11 May be bonded to each other to form an aryl or heteroaryl ring. At least one hydrogen of the formed aryl and heteroaryl rings is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, or is unsubstituted. The substituent when substituted is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted silane group. These groups are described as "substituted or unsubstituted", but where at least one hydrogen is substituted, preferably are aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, or substituted silyl groups. Further, the aryl group of the diarylamino group is substituted with an alkyl group or a cycloalkyl group, or is unsubstituted. For the first substituent and the second substituent, and for statements and preferred ranges thereof used herein, reference may be made to the description. As aryl radicals formedThe ring is preferably a benzene ring, a naphthalene ring, an indene ring, or a cyclopentadiene ring, and the heteroaryl ring formed is preferably a thiophene ring, a pyrrole ring, a furan ring, a benzothiophene ring, a benzofuran ring, or an indole ring.
In the formula (1), the ring C is a ring structure represented by the formula (C). Any two consecutive Z in formula (C) C In which one is with Y 1 A bound carbon, another being with X 2 A bonded carbon. I.e. Y 1 And X 2 Adjacent on ring C. This refers to any two consecutive Zs of the c1 ring as shown below C Can be reacted with Y 1 And X 2 A bond, and any two consecutive Z of the c2 ring C Can be reacted with Y 1 And X 2 Bonding. Preferred embodiments thereof will be described below. Preferably, in the formulae (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h), Z c Independently of each other are all C-R 11 In addition, in the formula (1 c), the formula (1 d), the formula (1 e), the formula (1 f), the formula (1 g) and the formula (1 h), Z of the c2 ring is also preferable c Each independently is all C-R c R's adjacent to each other as described later c Form a bond with each other to form an aryl ring (preferably a benzene ring). Among formulae (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h), formulae (1 a), (1 b) and (1 a) are preferable, and formula (1 a) is most preferable. Note that, for the description of each symbol and each phrase, the description of the present specification to be described later can be referred to.
[ solution 12]
Figure BDA0003615335190000151
In the formulae (1 a) to (1 h), X c Is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two of (1)The R's may be bonded to each other to form a ring, or may be not bonded to each other to form a ring. These groups are described as "substituted or unsubstituted", but where at least one hydrogen is substituted, preferably are aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, or substituted silyl groups. Furthermore, the aryl group of the diarylamino group is substituted with an alkyl group or a cycloalkyl group, or is unsubstituted. The first substituent and the second substituent, and the terms and preferred ranges thereof used herein can be referred to in the specification.
In the formulae (1 a) to (1 h), Z C Are each independently N or C-R C ，R C Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl.
These groups are described as "substituted or unsubstituted", but in the case where at least one hydrogen is substituted, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, or substituted silane groups are preferred. Further, the aryl group of the diarylamino group is substituted with an alkyl group or a cycloalkyl group, or is unsubstituted. For the first substituent and the second substituent, and for statements and preferred ranges thereof used herein, reference may be made to the description in the specification.
Two adjacent R C May be bonded to each other to form an aryl or heteroaryl ring. Substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted arylboronSubstituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl. The substituent when substituted is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted silane group. These groups are described as "substituted or unsubstituted", but in the case where at least one hydrogen is substituted, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, or substituted silane groups are preferred. Further, the aryl group of the diarylamino group is substituted with an alkyl group or a cycloalkyl group, or is unsubstituted. The aryl ring to be formed is preferably a benzene ring, a naphthalene ring, an indene ring, or a cyclopentadiene ring, and the heteroaryl ring to be formed is preferably a thiophene ring, a pyrrole ring, a furan ring, a benzothiophene ring, a benzofuran ring, or an indole ring, and most preferably a benzene ring. For the first substituent and the second substituent, and for statements and preferred ranges thereof used herein, reference may be made to the description in the specification.
In the formulae (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h), Z of the c2 ring is preferred C All are each independently N or C-R C And adjacent C-R C Form a bond with each other to form an aryl ring, or heteroaryl ring (preferably an aryl ring, more preferably a benzene ring). Preferred embodiments thereof will be described below. With respect to the definitions of the symbols of formula (1 c-2), formula (1 d-2), formula (1 e-2), formula (1 f-2), formula (1 g-2) and formula (1 h-2) and their preferred ranges, reference is made to the descriptions of formula (1 c), formula (1 d), formula (1 e), formula (1 f), formula (1 g) and formula (1 h).
[ solution 13]
Figure BDA0003615335190000171
In the formula (1) and preferred embodiments thereof, Y 1 Are respectively independentAnd is immediately B, P = O, P = S, al, ga, as, si-R, or Ge-R, preferably B or P = O, most preferably B. R of the Si-R and Ge-R is aryl with 6-12 carbon atoms, alkyl with 1-6 carbon atoms or cycloalkyl with 3-14 carbon atoms. Y of formula (1) 1 R in Si-R and Ge-R in (1) is an aryl group, an alkyl group or a cycloalkyl group, and the aryl group, the alkyl group or the cycloalkyl group may be exemplified by the groups mentioned above. Particularly preferred is an aryl group having 6 to 10 carbon atoms (e.g., phenyl group, naphthyl group, etc.), an alkyl group having 1 to 5 carbon atoms (e.g., methyl group, ethyl group, etc.), or a cycloalkyl group having 5 to 10 carbon atoms (preferably cyclohexyl group or adamantyl group).
In the formula (1), X 1 And X 2 One is > N-GA, the other > N-GB.
GA in N-GA is a monovalent group represented by the formula (GA).
[ chemical 14]
Figure BDA0003615335190000172
In the formula (GA), Z a Each independently is N or C-R a . Preferably all of Z a Are each independently C-R a 。R a Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl. As R a Preferably, it is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl. These radicals are stated as "substituted or unsubstituted", but in the case of at least one hydrogen being substituted, aryl, heteroaryl, diarylamino, cycloalkyl, or substituted silanes are preferredAnd the aryl group of the diarylamino group is substituted by alkyl or cycloalkyl, or is unsubstituted. These radicals are stated as "substituted or unsubstituted", but in the case of at least one hydrogen being substituted, aryl (at least one hydrogen being substituted or unsubstituted by alkyl or cycloalkyl), heteroaryl (at least one hydrogen being substituted or unsubstituted by alkyl or cycloalkyl), alkyl or cycloalkyl are preferred.
R a Most preferred is hydrogen or an alkyl group (particularly tR described later). Note that, as for the terms used herein and their preferred ranges, the description in the specification can be referred to. In the formula (GA), preferably zero to three R a Is a substituent other than hydrogen, other R a Is hydrogen, more preferably zero to two R a Is a substituent other than hydrogen, other R a Is hydrogen, more preferably zero to one R a Is a substituent other than hydrogen, other R a Is hydrogen.
In the formula (GA), two adjacent R a May be bonded to each other to form an aryl or heteroaryl ring. At least one hydrogen of the formed aryl and heteroaryl rings is replaced by R a (wherein, here, R is a Represents the case of hydrogen and R a Other than when they are bonded to each other to form a ring), or unsubstituted. As R substituted on at least one hydrogen of the aryl and heteroaryl rings formed a Preferably, it is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl. These groups are described as "substituted or unsubstituted," but in the case where at least one hydrogen is substituted, it is preferably aryl (at least one hydrogen is substituted or unsubstituted with alkyl or cycloalkyl), heteroaryl (at least one hydrogen is substituted or unsubstituted with alkyl or cycloalkyl), diarylamino (the aryl of diarylamino is substituted or unsubstituted with alkyl or cycloalkyl), alkyl, cycloalkyl, or a substituted silyl group, more preferably aryl, heteroaryl, alkyl, or cycloalkyl.
In the formula (GA), A is > O, > N-R, > Si (-R) 2 、＞C(-R) 2 S or SeR of said > N-R, said > Si (-R) 2 R of (b), and the & gtC (-R) 2 R of (a) is each independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, > Si (-R) 2 And said > C (-R) 2 R of (2) are bonded to each other to form a ring, or are not bonded to each other to form a ring. A is preferably > O, > N-R, > C (-R) 2 Or > S, more preferably > O or > N-R, most preferably > O. In addition, as for R > N-R as A, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group is preferable. These groups are described as "substituted or unsubstituted," but in the case where at least one hydrogen is substituted, it is preferably aryl (at least one hydrogen is substituted or unsubstituted with alkyl or cycloalkyl), heteroaryl (at least one hydrogen is substituted or unsubstituted with alkyl or cycloalkyl), diarylamino (the aryl of diarylamino is substituted or unsubstituted with alkyl or cycloalkyl), alkyl, cycloalkyl, or a substituted silyl group, more preferably aryl, heteroaryl, alkyl, or cycloalkyl.
A monovalent group represented by the formula (GA) and X as X at any position 1 Or X 2 N-GA. As the position of the formula (GA) bonded to N > N-GA, there can be mentioned: as Z a C-H (corresponding to C-R) a R of (A) a In the case of H), as Z a C-R of (A) a R of (A) to (B) a Any one of C (carbon atom) and adjacent C-R a Two of R a Any C (carbon atom), adjacent C-R on aryl or heteroaryl ring bonded to each other a Two of R a R as a substituent of an aryl or heteroaryl ring bonded to each other a Any one of C (carbon atom), any one of C (carbon atom) on a substituent of a monovalent group represented by the formula (GA), any one of C (carbon atom) on R > N-R as A, si (-R) as A 2 Any one of C (carbon atom) on R of (1), or > C (-R) as A 2 Any one of C (carbon atom) s in (1), preferably Z a C-H (corresponding to C-R) a R of (A) to (B) a In the case of H), or adjacent C-R a Two of R a Any C (carbon atom) on the aryl or heteroaryl ring bonded to each other.
Specific examples of the monovalent group represented by formula (GA) include monovalent groups represented by any one of the following formulae (GA-1) to (GA-52). Which are not limited to these examples. In the following formulae, X is 1 Or X 2 Is greater than the N-GA bond position. Note that, as to each symbol in the formula, the description in the specification can be referred to. In addition, at least one hydrogen of the monovalent groups represented by formulas (GA-1) to (GA-52) may be substituted with a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted diheteroarylamino group, a substituted or unsubstituted arylheteroarylamino group, a substituted or unsubstituted diarylboron group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group. The substituted group is most preferably an alkyl group (particularly tR described later) or a cycloalkyl group. These radicals are stated as "substituted or unsubstituted", but in the case of at least one hydrogen being substituted, they are preferably aryl, heteroaryl, diarylamino, alkyl, cycloalkyl or substituted silyl radicals, the aryl radical of the diarylamino radical being substituted by alkyl or cycloalkyl radicals, or being unsubstituted. These radicals are stated as "substituted or unsubstituted", but in the case of at least one hydrogen being substituted, aryl (at least one hydrogen being substituted or unsubstituted by alkyl or cycloalkyl), heteroaryl (at least one hydrogen being substituted or unsubstituted by alkyl or cycloalkyl), alkyl or cycloalkyl are preferred. The monovalent groups represented by the formulae (GA-1) to (GA-52) are not condensed with at least one cycloalkane described later, or are condensed with at least one cycloalkane described later.
The monovalent groups represented by the formulae (GA-1) to (GA-52) are preferably unsubstituted in any hydrogen (the monovalent groups represented by the formulae (GA-1) to (GA-52) have no substituent), or one or two hydrogens in the structure are substituted with an alkyl group (particularly tR described later) or a cycloalkyl group, and more preferably none of the hydrogens is substituted.
[ solution 15]
Figure BDA0003615335190000201
[ solution 16]
Figure BDA0003615335190000211
Among them, preferred is the formula (GA-1), the formula (GA-5), the formula (GA-6), the formula (GA-7), the formula (GA-8), the formula (GA-9), the formula (GA-10), the formula (GA-11), the formula (GA-12), or the formula (GA-13), more preferred is the formula (GA-1), the formula (GA-4), the formula (GA-6), or the formula (GA-7), and most preferred is the formula (GA-1) or the formula (GA-4).
In the formula (1), GB > N-GB is a monovalent group represented by the formula (GB).
[ chemical formula 17]
Figure BDA0003615335190000212
In the formula (GB), Z b Are each independently N or C-R b ，R b Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl. As R b Preferably substituted or unsubstituted aryl, substituted or unsubstituted heteroarylOr a substituted or unsubstituted cycloalkyl group. These groups are described as "substituted or unsubstituted," but in the case where at least one hydrogen is substituted, it is preferably aryl (at least one hydrogen is substituted or unsubstituted with alkyl or cycloalkyl), heteroaryl (at least one hydrogen is substituted or unsubstituted with alkyl or cycloalkyl), diarylamino (the aryl in diarylamino is substituted or unsubstituted with alkyl or cycloalkyl), alkyl, cycloalkyl, or a substituted silyl group, more preferably aryl, heteroaryl, alkyl, or cycloalkyl.
Z b Preferably independently of one another all are C-R b 。
R b Most preferred is hydrogen, an alkyl group (particularly tR described later) or an aryl group. The terms used herein and their preferred ranges can be referred to in the specification. In the formula (GB), preferably zero to four R b Is a substituent other than hydrogen, other R b Is hydrogen, more preferably zero to three R b Is a substituent other than hydrogen, other R b Is hydrogen, more preferably zero to two R b Is a substituent other than hydrogen, other R b Is hydrogen.
Two adjacent R b May be bonded to each other to form an aryl or heteroaryl ring. At least one hydrogen of the formed aryl and heteroaryl rings is independently via R b (wherein, here R b Represents the case of hydrogen and R b Except when bonded to each other to form a ring) or unsubstituted. As R substituted on at least one hydrogen of the formed aryl and heteroaryl rings b Preferably, it is a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl. These radicals are stated as "substituted or unsubstituted", but in the case of at least one hydrogen being substituted, preference is given to aryl (at least one hydrogen being substituted by alkyl or cycloalkyl or unsubstituted), heteroaryl (at least one hydrogen being substituted by alkyl or cycloalkyl or unsubstituted), diarylamino (the aryl of diarylamino being substituted by alkyl or cycloalkyl)Or unsubstituted), alkyl, cycloalkyl, or substituted silyl, more preferably aryl, heteroaryl, alkyl, or cycloalkyl.
A monovalent group represented by the formula (GB) is bonded to X at any position 1 Or X 2 An N bond > N-GB. Examples of any position in the formula (GB) to which an N-bond > N-GB is bonded include: as Z b C-H (corresponding to C-R) b R of (A) to (B) b In the case of H), as Z b C-R of (A) b R of (A) to (B) b Any one of C (carbon atom), adjacent C-R b R of (A) to (B) b Any C (carbon atom) or adjacent C-R on aryl or heteroaryl ring bonded to each other b Two of R b The substituents of aryl or heteroaryl rings being R b Any one of C (carbon atom) s is preferably Z b C-H (corresponding to C-R) b R of (A) b In the case of H), or adjacent C-R b R of (A) to (B) b Any C (carbon atom) on the aryl or heteroaryl ring bonded to each other.
Specific examples of the monovalent group represented by formula (GB) include monovalent groups represented by the following formulae (GB-1) to (GB-14). Which are not limited to these examples. In the following formulae, X is 1 Or X 2 A bonding position of N > N-GB. In addition, at least one hydrogen of the monovalent group represented by the formulae (GB-1) to (GB-14) may be substituted with a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted diheteroarylamino group, a substituted or unsubstituted arylheteroarylamino group, a substituted or unsubstituted diarylboron group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group. The substituent is most preferably an alkyl group (particularly tR described later) or a cycloalkyl group. These groups are described as "substituted or unsubstituted", butIn the case where at least one hydrogen is substituted, it is preferably aryl (at least one hydrogen is substituted with alkyl or cycloalkyl, or unsubstituted), heteroaryl (at least one hydrogen is substituted with alkyl or cycloalkyl, or unsubstituted), diarylamino (the aryl of diarylamino is substituted with alkyl or cycloalkyl, or unsubstituted), alkyl, cycloalkyl, or substituted silyl, more preferably aryl, heteroaryl, alkyl, or cycloalkyl. Further, at least one benzene ring in the monovalent groups represented by the formulae (GB-1) to (GB-14) is not condensed with at least one cycloalkane, or is condensed with at least one cycloalkane, as will be described later. The monovalent group represented by the formulae (GB-1) to (GB-14) is preferably a group having a structure in which none of the hydrogens is substituted (the monovalent group represented by the formulae (GB-1) to (GB-14) has no substituent), or one or two hydrogens in the structure are substituted with an alkyl group (particularly tR described later) or a cycloalkyl group. Structures in which at least one benzene ring of these groups is condensed with at least one cycloalkane are also preferable.
[ solution 18]
Figure BDA0003615335190000231
Among them, preferred is the formula (GB-1), the formula (GB-2), the formula (GB-3), the formula (GB-6), the formula (GB-7), the formula (GB-8), the formula (GB-12), the formula (GB-13), or the formula (GB-14), more preferred is the formula (GB-1), the formula (GB-2), the formula (GB-3), the formula (GB-6), the formula (GB-13), or the formula (GB-14), and most preferred is the formula (GB-1), the formula (GB-3), the formula (GB-6), the formula (GB-13), or the formula (GB-14).
The polycyclic aromatic compound of the present invention is a polycyclic aromatic compound having one or more structures containing the structural unit represented by formula (1) and the preferred forms thereof. Examples of the polycyclic aromatic compound having a structure including one of the structural units include polycyclic aromatic compounds represented by the structural unit represented by the formula (1) described above. Examples of the polycyclic aromatic compound having two or more structures containing the structural unit represented by formula (1) include compounds corresponding to the polymers of the polycyclic aromatic compound represented by the above-described formula as the structural unit represented by formula (1). The polymer is preferably a dimer to hexamer, more preferably a dimer to trimer, and particularly preferably a dimer. The polymer may be in a form having a plurality of the unit structures in one compound, and may be in a form in which the unit structures are bonded so as to share any of the rings (a ring, B ring, or C ring) included in the unit structures, or in a form in which the unit structures are bonded so as to condense any of the rings (a ring, B ring, or C ring) included in the unit structures. The above unit structure may be a plurality of units bonded by a single bond, a linking group having 1 to 3 carbon atoms such as alkylene, phenylene, or naphthylene. Among these, the preferred one is a form in which the bonds are bonded so as to share a ring.
At least one polycyclic aromatic compound having one or more structures including the structural unit represented by the formula (1) and preferably at least one selected from the group consisting of an aryl ring and a heteroaryl ring is not condensed with at least one cycloalkane or is condensed with at least one cycloalkane.
The cycloalkane may be any cycloalkane having 3 to 24 carbon atoms. At least one hydrogen in the cycloalkane may be substituted with an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkyl group having 1 to 24 carbon atoms or a cycloalkyl group having 3 to 24 carbon atoms, and at least one-CH in the cycloalkane 2 May be substituted by-O-and is preferably all-CH 2 -cycloalkanes.
When one or two or more structures containing the structural unit represented by formula (1) are condensed with at least one cycloalkane, at least one cycloalkane is a cycloalkane having 3 to 20 carbon atoms, and preferably a cycloalkane in which at least one hydrogen in the cycloalkane is substituted with an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 22 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms.
The "cycloalkane" preferably includes cycloalkanes having 3 to 24 carbon atoms, and more preferably includes, in order: cycloalkane having 3 to 20 carbon atoms, cycloalkane having 3 to 16 carbon atoms, cycloalkane having 3 to 14 carbon atoms, cycloalkane having 5 to 10 carbon atoms, cycloalkane having 5 to 8 carbon atoms, cycloalkane having 5 to 6 carbon atoms, and cycloalkane having 6 carbon atoms.
Specific cycloalkanes include: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, norbornene, bicyclo [1.1.0] butane, bicyclo [1.1.1] pentane, bicyclo [2.1.0] pentane, bicyclo [2.1.1] hexane, bicyclo [3.1.0] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, adamantane, diamantane, decahydronaphthalene and decahydroazulene, and alkyl (particularly methyl) substituents, halogen (particularly fluorine) substituents and deuterium substituents having 1 to 5 carbon atoms of these.
Among these, a structure in which at least one hydrogen on the carbon at the α -position of a cycloalkane (in a cycloalkyl group condensed on an aryl ring or a heteroaryl ring, the carbon at the position adjacent to the carbon at the condensation site corresponds to the benzyl position) is substituted, as shown in the following structural formula, is preferable, a structure in which two hydrogens on the carbon at the α -position are substituted is more preferable, and a structure in which four hydrogens in total on the two carbons at the α -position are substituted is still more preferable. This is to improve the durability of the compound by protecting chemically active sites. As the substituent, there may be mentioned: alkyl (especially methyl) substituted with 1 to 5 carbon atoms, halogen (especially fluorine) substituted, deuterium substituted, and the like. Particularly preferred is a structure in which a partial structure represented by the following formula (Z-11) is bonded to adjacent carbon atoms in an aryl ring or heteroaryl ring.
[ formula 19]
Figure BDA0003615335190000241
In the formula (Z-11), me represents a methyl group and X represents a bonding position.
The number of cycloalkanes condensed in an aryl ring or heteroaryl ring is preferably one to three, more preferably one or two, and still more preferably one. For example, examples in which one or more cycloalkanes are condensed in one benzene ring (phenyl group) are shown below. * Represents a bonding position, and the position may be any of carbons constituting a benzene ring and not constituting a cycloalkane. Cycloalkanes condensed as shown in the formula (Cy-1-4) and the formula (Cy-2-4) may be condensed with each other. The same applies to the case where the ring (group) to be condensed is an aryl ring or heteroaryl ring other than a benzene ring (phenyl group), and the case where the cycloalkane to be condensed is cyclopentane or a cycloalkane other than cyclohexane.
[ solution 20]
Figure BDA0003615335190000251
At least one-CH in cycloalkanes 2 -may be substituted by-O-. For example, one or more-CH groups in cycloalkane condensed in one benzene ring (phenyl group) are shown below 2 Examples of-O-substitution. The same applies to the case where the condensed ring (group) is an aromatic ring or a heteroaromatic ring other than a benzene ring (phenyl group), and the case where the cycloalkane to be condensed is cyclopentane or a cycloalkane other than cyclohexane.
[ solution 21]
Figure BDA0003615335190000252
At least one hydrogen in the cycloalkane may be substituted, and as the substituent, for example: aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkoxy, aryloxy, substituted silyl, deuterium, cyano or halogen, the details of which can be cited in the description of the substituent of the first in this specification. Among these substituents, preferred are alkyl groups (for example, alkyl groups having 1 to 6 carbon atoms), cycloalkyl groups (for example, cycloalkyl groups having 3 to 14 carbon atoms), halogens (for example, fluorine), deuterium, and the like. When the cycloalkyl group is substituted, the cycloalkyl group may be substituted to form a spiro structure, and the examples are shown below.
[ solution 22]
Figure BDA0003615335190000253
As a form of cycloalkane condensation, first, a form is given in which any of rings a, B, and C (ring C1 or ring C2) in a polycyclic aromatic compound having one or two or more structures containing a structural unit represented by formula (1) is condensed with cycloalkane.
As another form of the cycloalkane condensation, there may be mentioned a polycyclic aromatic compound having one or two or more structures containing a structural unit represented by the formula (1), and X is X in a preferred form thereof 1 And X 2 One of the GA > N-GA is in the form of condensed with cycloalkane, and X is 1 And X 2 One of the GB groups > N-GB is a form condensed with cycloalkane, and examples of the GB group having an aryl group or heteroaryl group in the formula (1), that is, a diarylamino group (condensed to an aryl moiety thereof), a carbazolyl group (condensed to a benzene ring moiety thereof) or a benzocarbazolyl group (condensed to a benzene ring moiety thereof) condensed with cycloalkane, an aryl group as a substituent condensed with cycloalkane, a heteroaryl group as a substituent condensed with cycloalkane, an aryl group as a partial structure of a substituent (for example, an aryl moiety of aryloxy) condensed with cycloalkane, and a heteroaryl group as a partial structure of a substituent (for example, a heteroaryl moiety of diheteroarylamine) condensed with cycloalkane are given. Examples of the diarylamino group include the groups described as the "first substituent" in the specification.
The polycyclic aromatic compound having one or two or more structures containing the structural unit represented by the formula (1) and a preferred embodiment thereof, and the cycloalkane condensation is preferably in the form of condensation in the ring A, the ring B, or the ring C, and more preferably in the form of condensation in the ring B or the ring C. The condensed form is also preferable in both ring B and ring C.
Further, by introducing a cycloalkane structure into the polycyclic aromatic compound of the present invention, a decrease in melting point or sublimation temperature can be expected. In the sublimation purification, which is almost indispensable as a purification method for a material for an organic device such as an organic EL element requiring high purity, the purification can be performed at a relatively low temperature, and thus thermal decomposition of the material or the like is avoided. In addition, since the vacuum deposition process, which is a powerful means for manufacturing organic devices such as organic EL elements, can be performed at a relatively low temperature, thermal decomposition of materials can be avoided, and as a result, high-performance organic devices can be obtained. Further, since the introduction of a cycloalkane structure improves the solubility in an organic solvent, it can be applied to the production of a device by a coating process. The present invention is not particularly limited to these principles. Therefore, in the polycyclic aromatic compound having one or two or more structures including the structural unit represented by the formula (1) and a preferred embodiment thereof, the cycloalkane condensation is preferably introduced.
All or a part of hydrogen in one or two or more structures including the structural unit represented by the formula (1) and a preferred form thereof is substituted with deuterium, cyano group, or halogen, or is unsubstituted.
For example, in one or more structures containing the structural unit represented by the formula (1) and preferred embodiments thereof, the substituent on ring A, ring B, ring C, ring A to ring C, and Y 1 R (= alkyl, cycloalkyl, aryl) when Si-R or Ge-R is used, and X 1 And X 2 GA > N-GA, or as X 1 And X 2 One of GB > N-GB is hydrogen substituted by deuterium, cyano or halogen, but these may be aryl or heteroaryl, all or part of which hydrogen is substituted by deuterium, cyano or halogen. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine, and further preferably fluorine. In particular, the form in which hydrogen is substituted with deuterium is preferable because stability of the compound is improved. Preferably one hydrogen is replaced by deuterium, more preferably a plurality of hydrogens are replaced by deuterium, even more preferably all hydrogens of the aromatic moiety are replaced by deuterium, most preferably all hydrogens are replaced by deuterium.
Examples of the "aryl ring" include aryl rings having 6 to 30 carbon atoms, preferably aryl rings having 6 to 16 carbon atoms, more preferably aryl rings having 6 to 12 carbon atoms, and particularly preferably aryl rings having 6 to 10 carbon atoms.
Specific "aryl ring" may include: benzene ring as monocyclic system, biphenyl ring as bicyclic system, condensed biphenylNaphthalene ring and indene ring of the ring system, terphenyl ring (m-terphenyl, o-terphenyl, p-terphenyl) as a tricyclic system, acenaphthene ring, fluorene ring, phenalene ring, phenanthrene ring, anthracene ring as a condensed tricyclic system, triphenylene ring, pyrene ring, tetracene ring, phenanthrene ring, anthracene ring as a condensed tetracyclic system,
Figure BDA0003615335190000261
Rings, perylene rings as condensed five-ring systems, pentacene rings, and the like. The fluorene ring, the benzfluorene ring, and the indene ring each include a structure in which a fluorene ring, a benzfluorene ring, a cyclopentane ring, and the like are spiro-bonded. In addition, two of the two hydrogens including a methylene group in the fluorene ring, the benzofluorene ring, and the indene ring are each substituted with an alkyl group such as a methyl group as a first substituent described later, and are formed into a ring such as a dimethylfluorene ring, a dimethylbenzene ring, or a dimethylindene ring.
Examples of the "heteroaryl ring" include a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, more preferably a heteroaryl ring having 2 to 20 carbon atoms, still more preferably a heteroaryl ring having 2 to 15 carbon atoms, and particularly preferably a heteroaryl ring having 2 to 10 carbon atoms. Examples of the "heteroaryl ring" include heterocyclic rings containing one to five heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
Specific examples of the "heteroaryl ring" include: <xnotran> , , , , , , , , , , , , , , , , , , 1H- , , , , 1H- , , , , , , , , , , , (carboline) , , , , , , (phenazasiline) , , , , , , , , , , , , , , , , , , , . </xnotran> In addition, it is also preferable that two of the two hydrogens of the methylene group are substituted with an alkyl group such as a methyl group as a first substituent described later to form a ring such as a dimethylacridine ring, a dimethylxanthene ring, or a dimethylthioxanthene ring. In addition, a bipyridyl ring, a phenylpyridine ring, a pyridylphenyl ring as a bicyclic system, a terpyridyl ring, a bispyridylphenyl ring as a tricyclic system, and a pyridylbiphenyl ring as a tricyclic system can also be exemplified as the "heteroaryl ring". In addition, the "heteroaryl ring" also includes a pyran ring.
In addition, the following formula (BO) is also included in the heteroaryl ring.
[ chemical No. 23]
Figure BDA0003615335190000271
At least one hydrogen in the "aryl ring" or "heteroaryl ring" may be substituted with a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted "diarylamino", a substituted or unsubstituted "diheteroarylamino", a substituted or unsubstituted "arylheteroarylamino", a substituted or unsubstituted "diarylboryl", a substituted or unsubstituted "alkyl", a substituted or unsubstituted "alkenyl", a substituted or unsubstituted "cycloalkyl", a substituted or unsubstituted "alkoxy", a substituted or unsubstituted "aryloxy", a substituted or unsubstituted "arylthio", or a substituted or unsubstituted "substituted silyl" as a first substituent.
Specifically, the "aryl group" is a monovalent group obtained by removing one hydrogen from the "aryl ring", and examples thereof include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, still more preferably aryl groups having 6 to 16 carbon atoms, particularly preferably aryl groups having 6 to 12 carbon atoms, and most preferably aryl groups having 6 to 10 carbon atoms.
The "heteroaryl group" is a monovalent group obtained by removing one hydrogen from the "heteroaryl ring", and examples thereof include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples of the heteroaryl group include heterocyclic rings containing one to five heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
With respect to the aryl or heteroaryl group of each of "substituted or unsubstituted diarylamino group", "substituted or unsubstituted diheteroarylamino group", "substituted or unsubstituted arylheteroarylamino group" as the first substituent, the groups described as the "aryl" or "heteroaryl" may be cited together with their preferred ranges.
In diarylamino groups, two aryl groups are not bonded to each other, or are bonded via a linking group. In the diheteroarylamino, two heteroaryl groups are not bonded to one another or are bonded via a linking group. In arylheteroarylamino, the aryl and heteroaryl groups are not bonded to each other or are bonded via a linking group. That is, in the case where only "diarylamino", "diheteroarylamino" or "arylheteroarylamino" is described in the present specification, unless otherwise specified, the following descriptions are added, respectively: "two aryl groups of the diarylamino group are not bonded to each other or bonded via a linking group", "two heteroaryl groups of the diheteroarylamino group are not bonded to each other or bonded via a linking group", and "aryl and heteroaryl groups of the arylheteroarylamino group are not bonded to each other or bonded via a linking group".
The expression "do not bond to each other or bond via a linking group" means that, for example, two phenyl groups of a diphenylamino group may form a bond via a linking group as shown below. In addition, the description also applies to diheteroarylamino and arylheteroarylamino groups formed from aryl or heteroaryl groups.
[ formula 24]
Figure BDA0003615335190000281
Specific examples of the linking group include: > O, > N-R X 、＞C(-R X ) 2 、＞Si(-R X ) 2 、＞S、＞CO、＞CS、＞SO、＞SO 2 And > Se, R X Each independently is alkyl, cycloalkyl, aryl or heteroaryl, which may be substituted with alkyl, cycloalkyl, aryl or heteroaryl, and additionally > C (-R) X ) 2 、＞Si(-R X ) 2 R in (1) X Can be via a single bond or a linking group X Y Bonded to form a ring. As X Y Examples thereof include: > O, > N-R Y 、＞C(-R Y ) 2 、＞Si(-R Y ) 2 、＞S、＞CO、＞CS、＞SO、＞SO 2 And > Se, R Y Each independently being an alkyl, cycloalkyl, aryl or heteroaryl group, which may be substituted by an alkyl, cycloalkyl, aryl or heteroaryl group. Wherein, in X Y Is > C (-R) Y ) 2 And > Si (-R) Y ) 2 In the case of (2), two R Y No further ring formation occurs due to the bonding. Further, as the linking group, an alkenylene group may be mentioned. Any hydrogen of the alkenylene group may independently pass through R X Substituted, R X Independently from each other, alkyl, cycloalkyl, substituted silyl, aryl and heteroaryl, which may be substituted with alkyl, cycloalkyl, substituted silyl, aryl.
The "alkyl group" as the first substituent may be either a straight chain or branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms. Preferably an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 8 carbon atoms (branched chain alkyl group having 3 to 8 carbon atoms), particularly preferably an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms), and most preferably an alkyl group having 1 to 5 carbon atoms (branched chain alkyl group having 3 to 5 carbon atoms).
Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl (t-amyl), n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl (1, 3-tetramethylbutyl) 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3, 5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and the like. Further, examples of the method include: <xnotran> 1- -1- ,1,1- ,1,1- ,1- -1- ,1,1,4- ,1,1,2- ,1,1- ,1,1- ,1,1- ,1,1,5- ,1- -1- ,1- -1,3- ,1,1,2,2- ,1- -1- ,1,1- ,1- -1- ,1,1,3- ,1- -1- ,1,1,2- ,1- -1,2,2- ,1- -1- ,1,1- . </xnotran>
As a substituent including the "alkyl group", a tertiary alkyl group represented by the following formula (tR) is one of particularly preferable substituents as a substituent for an aryl ring or a heteroaryl ring in the a ring, the B ring, and the C ring. The reason for this is that the intermolecular distance is increased by such bulky substituents, and thus the luminescence quantum yield (PLQY) is improved. Further, a tertiary alkyl group represented by the formula (tR) is also preferable as a second substituent to be substituted with another substituent. Specifically, a diarylamino group substituted with a tertiary alkyl group represented by (tR), a carbazolyl group substituted with a tertiary alkyl group represented by (tR) (preferably, an N-carbazolyl group), or a benzocarbazolyl group substituted with a tertiary alkyl group represented by (tR) (preferably, an N-benzocarbazolyl group) can be mentioned. Examples of the "diarylamino group" include groups described below as "the first substituent". Examples of the substitution pattern of the group of formula (tR) for the diarylamino group, the carbazolyl group, and the benzocarbazolyl group include those in which some or all of the hydrogen atoms of the aryl ring or the benzene ring are substituted with the group of formula (tR).
[ solution 25]
Figure BDA0003615335190000291
In the formula (tR), R a 、R b And R c Each independently represents an alkyl group having 1 to 24 carbon atoms, wherein-CH is an optional group in the alkyl group 2 -may be substituted with-O-, the group represented by formula (tR) being substituted at one position with at least one hydrogen in the structure comprising the structural unit represented by formula (1).
As R a 、R b And R c The "alkyl group having 1 to 24 carbon atoms" in (b) may be either a straight chain or branched chain, and examples thereof include: a straight-chain alkyl group having 1 to 24 carbon atoms, a branched chain alkyl group having 3 to 24 carbon atoms, an alkyl group having 1 to 18 carbon atoms (a branched chain alkyl group having 3 to 18 carbon atoms), an alkyl group having 1 to 12 carbon atoms (a branched chain alkyl group having 3 to 12 carbon atoms), an alkyl group having 1 to 6 carbon atoms (a branched chain alkyl group having 3 to 6 carbon atoms), and an alkyl group having 1 to 4 carbon atoms (a branched chain alkyl group having 3 to 4 carbon atoms).
R in formula (tR) of formula (1) a 、R b And R c The total number of carbon atoms of (b) is preferably 3 to 20 carbon atoms, and particularly preferably 3 to 10 carbon atoms.
As R a 、R b And R c Specific examples of the alkyl group in (1) include: <xnotran> , , , , , , , , , , , , ,1- ,4- -2- ,3,3- ,2- , ,1- , , ,1- ,2- ,2- , ,2,2- ,2,6- -4- ,3,5,5- , , ,1- , </xnotran>Dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl, and the like.
Examples of the group represented by formula (tR) include: <xnotran> , ,1- -1- ,1,1- ,1,1- ,1- -1- ,1,1,3,3- ,1,1,4- ,1,1,2- ,1,1- ,1,1- ,1,1- ,1,1,5- ,1- -1- ,1- -1,3- ,1,1,2,2- ,1- -1- ,1,1- ,1- -1- ,1,1,3- ,1- -1- ,1,1,2- ,1- -1,2,2- ,1- -1- ,1,1- . </xnotran> Of these, preferred are tert-butyl and tert-amyl.
In addition, as the "cycloalkyl group" as the first substituent, there can be mentioned: cycloalkyl group having 3 to 24 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 16 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, cycloalkyl group having 5 to 6 carbon atoms, cycloalkyl group having 5 carbon atoms and the like. The cyclohexyl group in the present specification includes, as will be described later, a polycyclic group such as an adamantyl group in addition to a monocyclic cyclohexyl group and the like.
As specific cycloalkyl groups, there may be mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, diadamantyl, decahydronaphthyl, decahydroazulenyl, and alkyl (particularly methyl) substituents having 1 to 5 carbon atoms of these groups.
The "alkenyl group" as the first substituent may be a linear alkenyl group having 2 to 24 carbon atoms or a branched alkenyl group having 4 to 24 carbon atoms. The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, still more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably an alkenyl group having 2 to 4 carbon atoms.
Specific "alkenyl" may include: vinyl, allyl, butadienyl, and the like.
Examples of the "alkoxy group" as the first substituent include a linear alkoxy group having 1 to 24 carbon atoms and a branched alkoxy group having 3 to 24 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms (branched alkoxy group having 3 to 18 carbon atoms), more preferably an alkoxy group having 1 to 12 carbon atoms (branched alkoxy group having 3 to 12 carbon atoms), yet more preferably an alkoxy group having 1 to 6 carbon atoms (branched alkoxy group having 3 to 6 carbon atoms), and particularly preferably an alkoxy group having 1 to 5 carbon atoms (branched alkoxy group having 3 to 5 carbon atoms).
Specific examples of the alkoxy group include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-pentoxy, hexoxy, heptoxy, octoxy and the like.
As the "aryloxy" as the substituent of the first group, a group in which hydrogen of-OH group is substituted with an aryl group, and the aryl group and preferred ranges thereof can be cited with reference to the group described.
As the "arylthio" group as the substituent of the first, a group in which hydrogen of-SH group is substituted with an aryl group is cited, and the aryl group and preferred ranges thereof can be cited with reference to the group described.
The "substituted silyl group" as the first substituent may be, for example, a silyl group substituted with three substituents selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group. Examples thereof include: trialkylsilyl groups, tricycloalkylsilyl groups, dialkylcycloalkylsilyl groups, alkylbicycloalkylsilyl groups, triarylsilyl groups, dialkylarylsilyl groups, and alkyldiarylsilyl groups.
As the "trialkylsilyl group", groups in which three hydrogens of the silyl group are independently substituted with an alkyl group are cited, and the alkyl group and the preferable range thereof can refer to the group described as the "alkyl group" in the substituent of the first group. The alkyl group which is preferred for substitution is an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-pentyl, and the like.
Specific examples of the trialkylsilyl group include: trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tributylsilyl group, tri-sec-butylsilyl group, tri-tert-pentylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, isopropyldimethylsilyl group, butyldimethylsilyl group, sec-butyldimethylsilyl group, tert-pentyldimethylsilyl group, methyldiethylsilyl group, propyldiethylsilyl group, isopropyldiethylsilyl group, butyldiethylsilyl group, sec-butyldiethylsilyl group, tert-pentyldiethylsilyl group, methyldipropylsilyl group, ethyldipropylsilyl group, butyldipropylsilyl group, sec-butyldipropylsilyl group, tert-pentyldipropylsilyl group, methyldiisopropylsilyl group, ethyldiisopropylsilyl group, butyldiisopropylsilyl group, sec-butyldiisopropylsilyl group, tert-pentyldiisopropylsilyl group, and the like.
As the "tricycloalkylsilyl group", there can be mentioned groups in which three hydrogens of the silyl group are each independently substituted with a cycloalkyl group, and the cycloalkyl group and preferred ranges thereof can refer to the groups described as the "cycloalkyl group" in the substituent of the first group. The cycloalkyl group preferred for substitution is a cycloalkyl group having 5 to 10 carbon atoms, and specific examples thereof include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, decahydronaphthyl, decahydroazulenyl, and the like.
Specific examples of the tricycloalkylsilyl group include tricyclopentylsilyl groups and tricyclohexylsilyl groups.
Specific examples of the dialkylcycloalkylsilyl group substituted with two alkyl groups and one cycloalkyl group and the alkylbicycloalkylsilyl group substituted with one alkyl group and two cycloalkyl groups include silyl groups substituted with a group selected from the specific alkyl groups and cycloalkyl groups.
Specific examples of the dialkylarylsilyl group substituted with two alkyl groups and one aryl group, the alkyldiarylsilyl group substituted with one alkyl group and two aryl groups, and the triarylsilyl group substituted with three aryl groups include a silyl group substituted with a group selected from the specific alkyl groups and aryl groups. Specific examples of the triarylsilyl group include a triphenylsilyl group.
In addition, as the "aryl group" in the "diarylboron group" in the substituent of the first group and the preferable range thereof, the description of the aryl group can be cited. In addition, the two aryl groups may be bonded via a single bond or a linking group. Examples of the linking group include: > C (-R) 2 O, > S, and > N-R. Here, > C (-R) 2 And R > N-R is aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy (above which is the first substituent), which may be further substituted with aryl, heteroaryl, alkyl, or cycloalkyl (above which is the second substituent), and as specific examples of these groups, mention may be made of aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy as the first substituent. In the case where the term "diarylboron group" is used herein, unless otherwise specified, the following descriptions are added: "the two aryl groups of the diarylboron group are not bonded to each other, or are bonded via a single bond or a linking group".
A substituted or unsubstituted "aryl group", a substituted or unsubstituted "heteroaryl group", a substituted or unsubstituted "diarylamino group" (in which two aryl groups are not bonded to each other or via a linking group), a substituted or unsubstituted "diheteroarylamino group", a substituted or unsubstituted "arylheteroarylamino group", a substituted or unsubstituted "diarylboron group", a substituted or unsubstituted "alkyl group", a substituted or unsubstituted "cycloalkyl group", a substituted or unsubstituted "alkenyl group", a substituted or unsubstituted "alkoxy group", a substituted or unsubstituted "aryloxy group", or a substituted or unsubstituted "arylthio group" as a first substituent (first substituent) is described as being substituted or unsubstituted, at least one of these may be substituted with a second substituent (second substituent). The second substituent is preferably, unless otherwise specified, as follows: specific examples of the aryl group, heteroaryl group, diarylamino group, alkyl group, cycloalkyl group, or substituted silane group can be described with reference to "aryl group", "heteroaryl group", "diarylamino group", "alkyl group", "cycloalkyl group", or "substituted silane group" as the first substituent. In the aryl or heteroaryl group as the second substituent, a structure in which at least one hydrogen of these is substituted with an aryl group such as a phenyl group (specifically, the above-mentioned group), an alkyl group such as a methyl group or a tert-butyl group (specifically, the above-mentioned group), or a cycloalkyl group such as a cyclohexyl group (specifically, the above-mentioned group) is also included in the aryl or heteroaryl group as the second substituent. For example, when the second substituent is a carbazolyl group, a carbazolyl group in which the hydrogen at the 9-position is substituted with an aryl group such as a phenyl group, an alkyl group such as a methyl group, or a cycloalkyl group such as a cyclohexyl group is also included in a heteroaryl group as the second substituent. The description may also be applied to the description of the other first substituent and second substituent in the present specification.
The emission wavelength can be adjusted by steric hindrance, electron donating property, and electron withdrawing property of the structure of the first substituent. The group represented by the following structural formula is preferable, and methyl, tert-butyl, tert-amyl, tert-octyl, neopentyl, adamantyl, phenyl, o-tolyl, p-tolyl, 2, 4-xylyl, 2, 5-xylyl, 2, 6-xylyl, 2,4, 6-mesityl, diphenylamino, di-p-tolylamino, bis (p- (tert-butyl) phenyl) amino, carbazolyl, 3, 6-dimethylcarbazolyl, 3, 6-di-tert-butylcarbazolyl and phenoxy are more preferable, and methyl, tert-butyl, tert-amyl, tert-octyl, neopentyl, adamantyl, phenyl, o-tolyl, 2, 6-xylyl, 2,4, 6-mesityl, diphenylamino, di-p-tolylamino, bis (p- (tert-butyl) phenyl) amino, carbazolyl, 3, 6-dimethylcarbazolyl and 3, 6-di-tert-butylcarbazolyl are further preferable. From the viewpoint of ease of synthesis, a group having a large steric hindrance is preferred for selective synthesis, and specifically, a tert-butyl group, a tert-amyl group, a tert-octyl group, an adamantyl group, an o-tolyl group, a p-tolyl group, a 2, 4-xylyl group, a 2, 5-xylyl group, a 2, 6-xylyl group, a 2,4, 6-mesityl group, a di-p-tolylamino group, a bis (p- (tert-butyl) phenyl) amino group, a 3, 6-dimethylcarbazolyl group, and a 3, 6-di-tert-butylcarbazolyl group are preferred.
In the following structural formulae, "Me" represents a methyl group, "tBu" represents a tert-butyl group, "tAm" represents a tert-pentyl group, "thoct" represents a tert-octyl group, and "-" represents a bonding position.
[ solution 26]
Figure BDA0003615335190000321
[ solution 27]
Figure BDA0003615335190000331
[ solution 28]
Figure BDA0003615335190000332
[ solution 29]
Figure BDA0003615335190000341
[ solution 30]
Figure BDA0003615335190000351
[ solution 31]
Figure BDA0003615335190000361
[ solution 32]
Figure BDA0003615335190000371
[ solution 33]
Figure BDA0003615335190000381
[ chemical 34]
Figure BDA0003615335190000391
[ solution 35]
Figure BDA0003615335190000401
[ solution 36]
Figure BDA0003615335190000411
[ solution 37]
Figure BDA0003615335190000421
The polycyclic aromatic compound having one or two or more structures containing the structural unit represented by the formula (1) and the preferred form thereof is preferably a structure containing at least one tertiary alkyl group (such as a tertiary butyl group or a tertiary pentyl group) represented by the formula (tR), a neopentyl group or an adamantyl group, and more preferably a structure containing a tertiary alkyl group (such as a tertiary butyl group or a tertiary pentyl group) represented by the formula (tR). The reason for this is that the intermolecular distance is increased by such bulky substituents, and thus the luminescent quantum yield (PLQY) is improved. In addition, as a substituent, a diarylamino group is also preferable. Furthermore, a diarylamino group substituted with a group of formula (tR), a carbazolyl group substituted with a group of formula (tR) (preferably an N-carbazolyl group), or a benzocarbazolyl group substituted with a group of formula (tR) (preferably an N-benzocarbazolyl group) is also preferable. Examples of the substitution pattern of the group of formula (tR) for the diarylamino group, the carbazolyl group, and the benzocarbazolyl group include those in which some or all of the hydrogen atoms of the aryl ring or the benzene ring are substituted with the group of formula (tR).
Further specific examples of the polycyclic aromatic compound represented by the formula (1) of the present invention include the following compounds. In the following structural formulae, "Me" represents a methyl group, "Et" represents an ethyl group, "tBu" represents a tert-butyl group, and "D" represents deuterium. The following configuration is an example.
[ solution 38]
Figure BDA0003615335190000431
[ chemical 39]
Figure BDA0003615335190000441
[ solution 40]
Figure BDA0003615335190000451
[ solution 41]
Figure BDA0003615335190000461
[ solution 42]
Figure BDA0003615335190000471
[ solution 43]
Figure BDA0003615335190000481
[ solution 44]
Figure BDA0003615335190000491
[ solution 45]
Figure BDA0003615335190000501
[ chemical formula 46]
Figure BDA0003615335190000511
[ solution 47]
Figure BDA0003615335190000521
[ solution 48]
Figure BDA0003615335190000531
[ solution 49]
Figure BDA0003615335190000541
[ solution 50]
Figure BDA0003615335190000551
[ solution 51]
Figure BDA0003615335190000561
[ solution 52]
Figure BDA0003615335190000571
[ Hua 53]
Figure BDA0003615335190000581
[ formula 54]
Figure BDA0003615335190000591
[ solution 55]
Figure BDA0003615335190000601
[ solution 56]
Figure BDA0003615335190000611
[ solution 57]
Figure BDA0003615335190000621
[ solution 58]
Figure BDA0003615335190000631
The polycyclic aromatic compound of the present invention can be produced by the following procedure.
Method for producing polycyclic aromatic compound
The polycyclic aromatic compound of the present invention having one or more structures containing the structural unit represented by the formula (1) basically utilizes a bonding group (containing X) first 1 Or X 2 Group (B) to bond the a ring (a ring) with the B ring (B ring) and the C ring (C ring), thereby producing an intermediate (first reaction), followed by the utilization of a bonding group (including Y) 1 The group (B) bonds the a ring (a ring), the B ring (B ring) and the C ring (C ring), thereby producing a final product (second reaction). In the first reaction, nucleophilic extraction may be used, for example, in the case of etherificationGeneral reactions such as a substitution Reaction and an Ullmann Reaction, and general reactions such as a Buchwald-Hartwig Reaction can be used in the case of an amination Reaction. In the second Reaction, a Tandem Hetero-Friedel-Crafts Reaction (consecutive aromatic electrophilic substitution Reaction, the same applies hereinafter) can be used. The target compound can be produced by using a raw material having a desired condensed ring at a certain part of the reaction step, or by adding a step of condensing a ring.
< method for producing intermediate 1 >
The polycyclic aromatic compound of the present invention can be produced by a production method comprising the following steps. For the following steps, reference is made to the description of International publication No. 2015/102118.
The following describes a reaction including the following reaction steps: using an organic base Compound for X in the following intermediate 1 1 And X 2 A reaction process of metallizing the halogen atom (Hal) in between; using a compound selected from the group consisting of Y 1 Halide of (2), Y 1 Of an aminated halide of, Y 1 Alkoxylates of (D) and Y 1 With Y 1 A reaction step of performing exchange; and using the bronsted base to utilize the Y by successive aromatic electrophilic substitution reactions 1 And a reaction step of bonding the B ring and the C ring.
[ chemical 59]
Figure BDA0003615335190000641
Examples of the metallizing agent used in the halogen-metal exchange reaction in the flow described so far include: alkyl lithium such as methyllithium, n-butyllithium, sec-butyllithium or tert-butyllithium, isopropylmagnesium chloride, isopropylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, and lithium chloride complex of isopropylmagnesium chloride known as a Tabo's Reagent (Turbo Grignard Reagent), and the like.
In addition, examples of the metallation reagent used in the ortho-position metal exchange reaction in the flow scheme described so far include, in addition to the above-mentioned reagents: organic base compounds such as lithium diisopropylamide, lithium tetramethylpiperidine, lithium hexamethyldisilazide, potassium hexamethyldisilazide, lithium chloride tetramethylpiperidylmagnesium-lithium chloride complex, tri-n-butyllithium magnesium chloride, and the like.
Further, as additives which promote the reaction when alkyllithium is used as a metallizing agent, there can be mentioned: n, N, N ', N' -tetramethylethylenediamine, 1, 4-diazabicyclo [2.2.2] octane, N, N-dimethylpropyleneurea, and the like.
In addition, as the lewis acid used in the above-described flow scheme, there can be mentioned: alCl 3 、AlBr 3 、AlF 3 、BF 3 -OEt 2 、BCl 3 、BBr 3 、GaCl 3 、GaBr 3 、InCl 3 、InBr 3 、In(OTf) 3 、SnCl 4 、SnBr 4 、AgOTf、ScCl 3 、Sc(OTf) 3 、ZnCl 2 、ZnBr 2 、Zn(OTf) 2 、MgCl 2 、MgBr 2 、Mg(OTf) 2 、LiOTf、NaOTf、KOTf、Me 3 SiOTf、Cu(OTf) 2 、CuCl 2 、YCl 3 、Y(OTf) 3 、TiCl 4 、TiBr 4 、ZrCl 4 、ZrBr 4 、FeCl 3 、FeBr 3 、CoCl 3 、CoBr 3 And the like. In addition, those having these lewis acids supported on a solid can be used in the same manner. In the present specification, "OTf" means "trifluoromethylsulfonyl" or "trifluoromethylsulfonate.
Further, as the bronsted acid used in the flow described so far, there can be mentioned: p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, carborane acid, trifluoroacetic acid, (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methane, hydrogen chloride, hydrogen bromide, hydrogen fluoride, and the like. Further, as the solid bronsted acid, there can be mentioned: ambarist (Amberlist) (trade name: dow Chemical), nafion (Nafion) (trade name: dupont), zeolite (zeolite), and imperial (taycare) (trade name: imperial (Tayca) inc.), and the like.
In addition, as amines that can be added in the heretofore described schemes, there can be mentioned: diisopropylethylamine, triethylamine, tributylamine, 1, 4-diazabicyclo [2.2.2] octane, N-dimethyl-p-toluidine, N-dimethylaniline, pyridine, 2, 6-lutidine, 2, 6-di-tert-butylamine, and the like.
In addition, as the solvent used in the flow described so far, there can be mentioned: o-dichlorobenzene, chlorobenzene, toluene, benzene, dichloromethane, chloroform, dichloroethylene, trifluorotoluene, decahydronaphthalene, cyclohexane, hexane, heptane, 1,2, 4-trimethylbenzene, xylene, diphenyl ether, anisole, cyclopentyl methyl ether, tetrahydrofuran, dioxane, methyl-t-butyl ether, and the like.
Here, Y is described 1 B is exemplified, but Y can also be synthesized by appropriately changing the raw materials 1 A compound that is P, P = O, P = S, al, ga, as, si-R, or Ge-R.
In the scheme, a bronsted base or a lewis acid may be used to promote the tandem heterofriedel-crafts reaction. Wherein, Y is used 1 Of (b) a trifluoride, Y 1 Trichloride of (a) and Y 1 Tribromide of (5), Y 1 Y being triiodide or the like 1 In the case of the halide of (3), since an acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide is generated as the aromatic electrophilic substitution reaction proceeds, it is effective to use a bronsted base which traps an acid. On the other hand, in the use of Y 1 Of an aminated halide of, Y 1 In the case of the alkoxylate (b), since an amine or an alcohol is generated as the aromatic electrophilic substitution reaction proceeds, the bronsted base is not required in many cases, but since the releasing ability of the amino group or the alkoxy group is low, it is effective to use a lewis acid for promoting the release.
The polycyclic aromatic compound of the present invention also includes a compound in which at least a part of hydrogen atoms is substituted with deuterium or cyano group, or a compound substituted with halogen such as fluorine or chlorine, and such a compound can be synthesized in the same manner as described above by using a raw material in which a desired position is deuterated, cyanated, fluorinated, or chlorinated.
< 2. Organic device
The polycyclic aromatic compound of the present invention is useful as a material for organic devices. Examples of the organic device include: organic electroluminescent devices, organic field effect transistors, organic thin film solar cells, and the like.
The polycyclic aromatic compound and the polymer thereof of the present invention can be used as a material for an organic device. Examples of the organic device include: an organic electroluminescent device, an organic field effect transistor, an organic thin film solar cell, or the like, but an organic electroluminescent device is preferable. The polycyclic aromatic compound and the polymer thereof of the present invention are preferably a material for an organic electroluminescent element, more preferably a material for a light-emitting layer (light-emitting material), and most preferably a dopant material for a light-emitting layer.
< 2-1. Organic electroluminescent element
< 2-1-1. Structure of organic electroluminescent element
Fig. 1 is a schematic cross-sectional view showing an example of an organic EL element.
The organic EL element 100 shown in fig. 1 includes: the light-emitting device comprises a substrate 101, an anode 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode 102, a hole transport layer 104 disposed on the hole injection layer 103, a light-emitting layer 105 disposed on the hole transport layer 104, an electron transport layer 106 disposed on the light-emitting layer 105, an electron injection layer 107 disposed on the electron transport layer 106, and a cathode 108 disposed on the electron injection layer 107.
In addition, the organic EL element 100 may be formed by reversing the manufacturing procedure to have, for example, a structure including: the organic light emitting diode comprises a substrate 101, a cathode 108 arranged on the substrate 101, an electron injection layer 107 arranged on the cathode 108, an electron transport layer 106 arranged on the electron injection layer 107, a light emitting layer 105 arranged on the electron transport layer 106, a hole transport layer 104 arranged on the light emitting layer 105, a hole injection layer 103 arranged on the hole transport layer 104, and an anode 102 arranged on the hole injection layer 103.
All of the layers are not indispensable, and the minimum structural unit is a structure including the anode 102, the light-emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection layer 107 are layers that can be arbitrarily provided. In addition, each of the layers may include a single layer, or may include a plurality of layers.
As the form of the layers constituting the organic EL element, in addition to the structural form of the above-mentioned "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", the structure may be "substrate/anode/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/light-emitting layer/electron injection layer/cathode".
< 2-1-2. Light-emitting layer in organic electroluminescent element
The polycyclic aromatic compound of the present invention is preferably used as a material for forming any one or more organic layers in an organic electroluminescent element, and more preferably used as a material for forming a light-emitting layer. The light-emitting layer 105 emits light by recombination of holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound (light-emitting compound) which emits light by being excited by recombination of holes and electrons, and is preferably a compound which can be formed into a stable thin film shape and which exhibits strong light emission (fluorescence) efficiency in a solid state. The polycyclic aromatic compound of the present invention is useful as a material for a light-emitting layer, a dopant material, or a host material, but is preferably used as a material for a light-emitting layer, and more preferably used as a dopant material.
In addition, although the dopant is used in combination with an auxiliary dopant and an emitting dopant, the dopant is referred to as a light-emitting dopant used alone when it is simply referred to as "dopant" in the present specification.
The light-emitting layer may be a single layer or may include a plurality of layers, and each of the layers is formed of a material (host material or dopant material) for the light-emitting layer. The host material and the dopant material may be one kind or a combination of plural kinds, respectively. The dopant material may be included in the bulk of the host material or may be included in a portion of the host material, either. The doping method may be a co-evaporation method with the host material, or may be a method in which the host material is mixed in advance and then evaporated at the same time.
< dopant Material >
The polycyclic aromatic compound of the present invention can be preferably used as a dopant material.
Examples of dopant materials other than the polycyclic aromatic compound of the present invention are shown below. The following dopant materials are also preferably used in combination with the polycyclic aromatic compound of the present invention.
[ solution 60]
Figure BDA0003615335190000671
[ solution 61]
Figure BDA0003615335190000672
[ solution 62]
Figure BDA0003615335190000681
[ solution 63]
Figure BDA0003615335190000691
The amount of the dopant material used differs depending on the type of the dopant material, and may be determined by matching the characteristics of the dopant material. The amount of the dopant used is preferably 0.001 to 50 mass%, more preferably 0.05 to 20 mass%, and still more preferably 0.1 to 10 mass% of the total amount of the material for the light-emitting layer. In the above range, for example, concentration quenching is preferably prevented.
< host Material >
As the host material, anthracene, pyrene, dibenzo known as a light-emitting body from the past can be mentioned
Figure BDA0003615335190000692
Or a condensed ring derivative such as fluorene, a bisstyryl derivative such as a bisstyrylanthracene derivative or a distyrylbenzene derivative, a tetraphenylbutadiene derivative, a cyclopentadiene derivative, a fluorene derivative, a benzofluorene derivative, etc.
As the host material, for example, a compound represented by any one of the following formulae (H1), (H2), and (H3) can be used.
[ solution 64]
Figure BDA0003615335190000701
In the formulae (H1), (H2) and (H3), L 1 The arylene group having 6 to 24 carbon atoms, the heteroarylene group having 2 to 24 carbon atoms, the heteroarylene arylene group having 6 to 24 carbon atoms and the aryleneheteroarylene group having 6 to 24 carbon atoms are preferable, the arylene group having 6 to 16 carbon atoms is more preferable, the arylene group having 6 to 12 carbon atoms is even more preferable, the arylene group having 6 to 10 carbon atoms is particularly preferable, and specific examples thereof include divalent groups such as a benzene ring, a biphenyl ring, a terphenyl ring and a fluorene ring. The heteroarylene group is preferably a heteroarylene group having 2 to 24 carbon atoms, more preferably a heteroarylene group having 2 to 20 carbon atomsHeteroaryl, more preferably a heteroarylene group having 2 to 15 carbon atoms, particularly preferably a heteroarylene group having 2 to 10 carbon atoms, and specific examples thereof include: a divalent group such as a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a oxazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxathiin ring, a phenoxazine ring, a phenothiazine ring, an indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a furazan ring, and a thianthrene ring. At least one hydrogen in the compounds represented by the formulae may be substituted with an alkyl group having 1 to 6 carbon atoms, a cyano group, a halogen or deuterium.
Preferred specific examples include compounds represented by any of the following structural formulae. In the structural formulae given below, at least one hydrogen may be substituted with a halogen, a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group or a tert-butyl group), a phenyl group, a naphthyl group, or the like.
[ solution 65]
Figure BDA0003615335190000702
[ solution 66]
Figure BDA0003615335190000711
[ solution 67]
Figure BDA0003615335190000712
[ solution 68]
Figure BDA0003615335190000721
The amount of the host material to be used differs depending on the type of the host material, and may be determined in accordance with the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999 mass%, more preferably 80 to 99.95 mass%, and still more preferably 90 to 99.9 mass% of the total of the light-emitting layer material.
< Anthracene Compound >
Examples of the anthracene compound as a host include a compound represented by the formula (3-H) and a compound represented by the formula (3-H2).
[ solution 69]
Figure BDA0003615335190000722
In the formula (3-H),
x and Ar 4 Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, optionally substituted diheteroarylamino, optionally substituted arylheteroarylamino, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted arylthio or substituted silyl, all X and Ar 4 Will not be simultaneously hydrogen.
At least one hydrogen in the compound represented by formula (3-H) is substituted with halogen, cyano, deuterium, or a substituted heteroaryl, or is unsubstituted.
Further, the structure represented by the formula (3-H) may be used as a unit structure to form a polymer (preferably a dimer). In this case, for example, the unit structures represented by the formula (3-H) are bonded to each other via X, and X includes a single bond, an arylene group (e.g., a phenylene group, a biphenylene group, and a naphthylene group), and a heteroarylene group (e.g., a group having a divalent bond valence such as a pyridine ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring, and a phenyl-substituted carbazole ring).
The details of each group in the compound represented by the formula (3-H) can be described with reference to the formula (1), and further described in the following preferred embodiment column.
Preferred embodiments of the anthracene compound will be described below. The symbols in the following structures are defined as described above.
[ solution 70]
Figure BDA0003615335190000731
In formula (3-H), X is independently a group represented by formula (3-X1), formula (3-X2) or formula (3-X3), and the group represented by formula (3-X1), formula (3-X2) or formula (3-X3) is bonded to the anthracene ring of formula (3-H) at the position of X. Preferably, two xs do not simultaneously form a group represented by the formula (3-X3). More preferably, both X's do not simultaneously form a group represented by the formula (3-X2).
Further, the structure represented by the formula (3-H) may be used as a unit structure to form a polymer (preferably a dimer). In this case, for example, the unit structures represented by the formula (3-H) may be bonded to each other via X, and X may be a single bond, an arylene group (e.g., phenylene, biphenylene, and naphthylene), a heteroarylene group (e.g., a group having a divalent bond valence such as a pyridine ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring, and a phenyl-substituted carbazole ring), or the like.
The naphthylene moiety in the formulae (3-X1) and (3-X2) may be condensed with a benzene ring. The structure condensed in this manner is as follows.
[ solution 71]
Figure BDA0003615335190000741
Ar 1 And Ar 2 Each independently hydrogen, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl,Phenanthryl, fluorenyl, benzofluorenyl, fluorenyl,
Figure BDA0003615335190000742
A triphenylene group, a pyrenyl group, or a group represented by the formula (A) (including a carbazolyl group, a benzocarbazolyl group, and a phenyl-substituted carbazolyl group). In addition, in Ar 1 Or Ar 2 In the case of the group represented by the formula (A), the group represented by the formula (A) is bonded to the naphthalene ring in the formula (3-X1) or the formula (3-X2) at the position.
Ar 3 Is phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, fluorenyl, or the like,
Figure BDA0003615335190000743
A triphenylene group, a pyrenyl group, or a group represented by the formula (A) (including a carbazolyl group, a benzocarbazolyl group, and a phenyl-substituted carbazolyl group). In addition, in Ar 3 In the case of the group represented by formula (a), the group represented by formula (a) is bonded to a single bond represented by a straight line in formula (3-X3) at the position indicated by a letter X. That is, the anthracene ring of the formula (3-H) is directly bonded to the group represented by the formula (A).
In addition, ar 3 May have a substituent, ar 3 Wherein at least one hydrogen atom in the above-mentioned group (B) may be further substituted by an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group,
Figure BDA0003615335190000744
A triphenylene group, a pyrenyl group, or a group represented by the formula (A) (including a carbazolyl group and a phenyl-substituted carbazolyl group). In addition, in Ar 3 When the substituent is a group represented by formula (A), the group represented by formula (A) is bonded to Ar in formula (3-X3) 3 Bonding.
Ar 4 Each independently represents hydrogen, phenyl, biphenyl, terphenyl, naphthyl, or a silyl group substituted with an alkyl group having 1 to 4 carbon atoms (methyl, ethyl, tert-butyl, etc.) and/or a cycloalkyl group having 5 to 10 carbon atoms.
Examples of the alkyl group having 1 to 4 carbon atoms substituted in the silyl group include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclobutyl and the like, and three hydrogens of the silane group are independently substituted with these alkyl groups.
Specific "silyl group substituted with an alkyl group having 1 to 4 carbon atoms" includes: trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, isopropyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, tert-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, isopropyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, tert-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, tert-butyldipropylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, butyldiisopropylsilyl, sec-butyldiisopropylsilyl, tert-butyldiisopropylsilyl, and the like.
Examples of the cycloalkyl group having 5 to 10 carbon atoms substituted in the silyl group include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornenyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, decahydronaphthyl, decahydroazulenyl and the like, and three hydrogens in the silane group are each independently substituted with these cycloalkyl groups.
Specific examples of the "silyl group substituted with a cycloalkyl group having 5 to 10 carbon atoms" include tricyclopentylsilyl group and tricyclohexylsilyl group.
Examples of the substituted silyl group include a dialkylcycloalkylsilyl group substituted with two alkyl groups and one cycloalkyl group, and an alkylbicycloalkylsilyl group substituted with one alkyl group and two cycloalkyl groups.
Further, hydrogen in the chemical structure of the anthracene compound represented by the formula (3-H) may be substituted with a group represented by the formula (a). In the case of substitution with a group represented by formula (a), the group represented by formula (a) is substituted at said x with at least one hydrogen in the compound represented by formula (3-H).
The group represented by the formula (A) is one of substituents which the anthracene compound represented by the formula (3-H) may have.
[ chemical formula 72]
Figure BDA0003615335190000751
In the formula (A), Y is-O-, -S-or > N-R 29 ，R 21 ～R 28 Each independently hydrogen, alkyl which may be substituted, cycloalkyl which may be substituted, aryl which may be substituted, heteroaryl which may be substituted, alkoxy which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkylbicycloalkylsilyl, amino which may be substituted, halogen, hydroxy or cyano, R 21 ～R 28 In which adjacent radicals may be bonded to one another to form a hydrocarbon, aryl or heteroaryl ring, R 29 Is hydrogen or a substituted aryl group.
Y in the formula (A) is preferably-O-.
As R 21 ～R 28 The "alkyl group" of the "alkyl group which may be substituted" in (1) may be either a straight chain or branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms. Preferably an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms), and particularly preferably an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms).
Specific examples of the "alkyl group" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3, 5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and the like.
As R 21 ～R 28 The "cycloalkyl group" of the "cycloalkyl group which may be substituted" in (1) includes: cycloalkyl group having 3 to 24 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 16 carbon atoms, cycloalkyl group having 3 to 14 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, cycloalkyl group having 5 to 6 carbon atoms, cycloalkyl group having 5 carbon atoms and the like.
Specific "cycloalkyl" groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and an alkyl (particularly methyl) substituent having 1 to 4 carbon atoms of these groups, or norbornenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [2.1.1] hexyl, bicyclo [3.1.0] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl, decahydroazulenyl, and the like.
As R 21 ～R 28 The "aryl group" of the "aryl group which may be substituted" in (1) includes, for example, an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms.
Specific "aryl" groups include: phenyl as a monocyclic system, biphenyl as a bicyclic system, naphthyl as a condensed bicyclic system, terphenyl (m-terphenyl, o-terphenyl, p-terphenyl) as a tricyclic system, acenaphthyl, fluorenyl, phenaenyl, phenanthryl as a condensed tricyclic system, triphenylene, pyrenyl, tetracenyl as a condensed tetracyclic system, perylenyl, pentacenyl as a condensed pentacyclic system, and the like.
As R 21 ～R 28 The "heteroaryl group" of the "heteroaryl group which may be substituted" in (1) includes, for example, carbon atomsThe heteroaryl group having 2 to 30 carbon atoms is preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples of the heteroaryl group include heterocyclic rings containing one to five heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.
Specific examples of the "heteroaryl group" include: pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiyl, phenoxazinyl, phenothiazinyl, phenazinyl, indolizinyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzo [ b ] thienyl, dibenzothienyl, furazanyl, thianthrenyl, naphthobenzofuryl, naphthobenzothienyl, and the like.
As R 21 ～R 28 Examples of the "alkoxy group" of the "alkoxy group which may be substituted" in (1) include a linear alkoxy group having 1 to 24 carbon atoms and a branched alkoxy group having 3 to 24 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms (a branched alkoxy group having 3 to 18 carbon atoms), more preferably an alkoxy group having 1 to 12 carbon atoms (a branched alkoxy group having 3 to 12 carbon atoms), yet more preferably an alkoxy group having 1 to 6 carbon atoms (a branched alkoxy group having 3 to 6 carbon atoms), and particularly preferably an alkoxy group having 1 to 4 carbon atoms (a branched alkoxy group having 3 to 4 carbon atoms).
Specific "alkoxy" may include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
As R 21 ～R 28 The "aryloxy group" of the "aryloxy group which may be substituted" in (1),radicals in which hydrogen is an-OH group substituted by aryl radicals, which radicals may be cited as R 21 ～R 28 The "aryl group" in (1).
As R 21 ～R 28 The "arylthio group" of the "arylthio group which may be substituted" in (1) is a group in which hydrogen of the-SH group is substituted with an aryl group which may be cited as R 21 ～R 28 The "aryl" in (1).
As R 21 ～R 28 As the "trialkylsilyl group" in (1), there can be mentioned groups in which three hydrogens of the silyl group are each independently substituted with an alkyl group, and the alkyl group may be cited as R 21 ～R 28 The "alkyl" in (1) or (b). The alkyl group preferred for substitution is an alkyl group having 1 to 4 carbon atoms, and specifically, there may be mentioned: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclobutyl and the like.
Specific examples of the "trialkylsilyl group" include: trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, isopropyldimethylsilyl, butyldimethylsilyl, sec-butyldimethylsilyl, tert-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, isopropyldiethylsilyl, butyldiethylsilyl, sec-butyldiethylsilyl, tert-butyldiethylsilyl, methyldipropylsilyl, ethyldipropylsilyl, butyldipropylsilyl, sec-butyldipropylsilyl, tert-butyldipropylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, butyldiisopropylsilyl, sec-butyldiisopropylsilyl, tert-butyldiisopropylsilyl, and the like.
As R 21 ～R 28 As the "tricycloalkylsilyl group" in (1), there can be mentioned a group in which three hydrogens in the silyl group are each independently substituted with a cycloalkyl group, which may be cited as R 21 ～R 28 The "cycloalkyl" in (1) above. For substitutionThe preferred cycloalkyl group is a cycloalkyl group having 5 to 10 carbon atoms, and specifically, there may be mentioned: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo [1.1.1]Pentyl, bicyclo [2.1.0]]Pentyl, bicyclo [2.1.1] s]Hexyl, bicyclo [3.1.0]Hexyl, bicyclo [2.2.1]Heptyl, bicyclo [2.2.2]Octyl, adamantyl, decahydronaphthyl, decahydroazulenyl, and the like.
Specific examples of the "tricycloalkylsilyl group" include tricyclopentylsilyl group and tricyclohexylsilyl group.
Specific examples of the dialkylcycloalkylsilyl group substituted with two alkyl groups and one cycloalkyl group and the alkylbicycloalkylsilyl group substituted with one alkyl group and two cycloalkyl groups include silyl groups substituted with a group selected from the specific alkyl groups and cycloalkyl groups.
As R 21 ～R 28 The "substituted amino group" of the "amino group which may be substituted" in (1) includes, for example, an amino group in which two hydrogens are substituted with an aryl group or a heteroaryl group. Two hydrogen aryl substituted amino groups are diaryl (two aryl groups are not bonded to each other or may be bonded through a linker) substituted amino groups, two hydrogen heteroaryl substituted amino groups are diheteroaryl substituted amino groups, and two hydrogen aryl and heteroaryl substituted amino groups are arylheteroaryl substituted amino groups. The aryl or heteroaryl groups may be referred to as R 21 ～R 28 The "aryl" or "heteroaryl" in (1).
Specific "substituted amino group" includes: diphenylamino, dinaphthylamino, phenylnaphthylamino, bipyrylamino, phenylpyridylamino, naphthylpyridylamino and the like.
As R 21 ～R 28 Examples of the "halogen" in (1) include: fluorine, chlorine, bromine, iodine.
As R 21 ～R 28 Some of the groups described above may be substituted as described above, and examples of the substituent in the above case include: alkyl, cycloalkyl, aryl or heteroaryl. The alkyl, cycloalkyl, aryl or heteroaryl groups may be cited as R 21 ～R 28 The "alkyl group" or "cycloalkane" in (1)Radicals "," aryl "or" heteroaryl ".
"> N-R as Y 29 R in ` 29 Is hydrogen or a substituted aryl group, and as said aryl group, the reference may be made to R 21 ～R 28 The substituent mentioned for the "aryl" in (1) may be cited as the substituent mentioned for R 21 ～R 28 The substituent(s) of (1).
R 21 ～R 28 Wherein adjacent groups may be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring. The case where no ring is formed is a group represented by the following formula (A-1), and examples of the case where a ring is formed include groups represented by the following formulae (A-2) to (A-14). Further, at least one hydrogen in the group represented by any one of the formulae (a-1) to (a-14) may be substituted with an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, an arylthio group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, an alkylbicycloalkylsilyl group, a diaryl group (two aryl groups are not bonded to each other or may be bonded via a linking group), a substituted amino group, a diheteroaryl substituted amino group, an arylheteroaryl substituted amino group, a halogen, a hydroxyl group, or a cyano group.
[ solution 73]
Figure BDA0003615335190000781
As the ring formed by bonding adjacent groups to each other, a hydrocarbon ring may be mentioned, for example, a cyclohexane ring, and as the aryl ring or heteroaryl ring, the above-mentioned R 21 ～R 28 The "aryl group" or "heteroaryl group" in (1) is a ring structure formed by condensation with one or two benzene rings in the formula (A-1).
The group represented by formula (a) is a group obtained by removing one hydrogen at any position of formula (a), and represents the position. That is, any position of the group represented by the formula (A) may be a bonding position. For example, the carbon atoms may be bonded to any of two benzene rings in the structure of the formula (A), or R in the structure of the formula (A) 21 ～R 28 Wherein adjacent groups are bonded to each other to form an atom on any ring, or "> N-R as Y in the structure of the formula (A) 29 R in ` 29 In any position of, "> N-R 29 N (R) in 29 A bond) directly bonded. The same applies to the groups represented by any one of the formulae (A-1) to (A-14).
Examples of the group represented by formula (A) include a group represented by any one of formulae (A-1) to (A-14), preferably a group represented by any one of formulae (A-1) to (A-5) and formulae (A-12) to (A-14), more preferably a group represented by any one of formulae (A-1) to (A-4), even more preferably a group represented by any one of formulae (A-1), (A-3) and (A-4), and particularly preferably a group represented by formula (A-1).
Examples of the group represented by the formula (a) include the following groups. Y and x in the formula are as defined above.
[ chemical formula 74]
Figure BDA0003615335190000791
[ solution 75]
Figure BDA0003615335190000792
In the compound represented by the formula (3-H), the group represented by the formula (A) is preferably a group bonded to the naphthalene ring in the formula (3-X1) or the formula (3-X2), the single bond in the formula (3-X3), or Ar in the formula (3-X3) 3 Any of the above forms of bonds.
In addition, all or a part of hydrogen in the chemical structure of the anthracene compound represented by the formula (3-H) may be deuterium.
The anthracene compound serving as a host may be, for example, a compound represented by the following formula (3-H2).
[ 76]
Figure BDA0003615335190000801
Formula (A), (B) and3-H2) of Ar c Is optionally substituted aryl or optionally substituted heteroaryl, R c Is hydrogen, alkyl, or cycloalkyl, ar 11 、Ar 12 、Ar 13 、Ar 14 、Ar 15 、Ar 16 、Ar 17 And Ar 18 Each independently hydrogen, aryl which may be substituted, heteroaryl which may be substituted, diarylamino which may be substituted, diheteroarylamino which may be substituted, arylheteroarylamino which may be substituted, alkyl which may be substituted, cycloalkyl which may be substituted, alkenyl which may be substituted, alkoxy which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, or silyl which may be substituted, at least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano, or deuterium.
The definition of "aryl group which may be substituted", "heteroaryl group which may be substituted", "diarylamino group which may be substituted", "diheteroarylamino group which may be substituted", "arylheteroarylamino group which may be substituted", "alkyl group which may be substituted", "cycloalkyl group which may be substituted", "alkenyl group which may be substituted", "alkoxy group which may be substituted", "aryloxy group which may be substituted", "arylthio group which may be substituted", or "silyl group which may be substituted" in the formula (3-H2) is the same as that shown in the formula (3-H), and the description in the formula (1) can be cited.
The "optionally substituted aryl" is preferably a group represented by any one of the following formulae (3-H2-X1) to (3-H2-X8).
[ chemical 77]
Figure BDA0003615335190000802
In the formulae (3-H2-X1) to (3-H2-X8), a bond site is represented. In the formulae (3-H2-X1) to (3-H2-X3), ar 21 、Ar 22 And Ar 23 Each independently is hydrogen, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, or,
Figure BDA0003615335190000803
A phenyl group, a triphenylene group, a pyrenyl group, an anthracenyl group, or a group represented by the formula (A). In the description of the formula (3-H2), the group represented by the formula (A) is the same as the group described for the anthracene compound represented by the formula (3-H).
In the formulae (3-H2-X4) to (3-H2-X8), ar 24 、Ar 25 、Ar 26 、Ar 27 、Ar 28 、Ar 29 And Ar 30 Each independently hydrogen, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl,
Figure BDA0003615335190000812
A triphenylene group, a pyrenyl group, or a group represented by the formula (A). Further, any one or two or more hydrogens of the groups represented by the formulae (3-H2-X1) to (3-H2-X8) may be substituted with an alkyl group having 1 to 6 carbon atoms (preferably, a methyl group or a tert-butyl group).
Further, preferable examples of the "aryl group which may be substituted" include those which may be substituted by a substituent selected from the group consisting of phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, fluorenyl group, etc,
Figure BDA0003615335190000813
A terphenyl group (particularly an m-terphenyl-5' -group) substituted with at least one substituent group selected from the group consisting of a triphenylene group, a pyrenyl group and a group represented by the formula (A).
Examples of the "heteroaryl group which may be substituted" may also include a group represented by the formula (A). In addition, as specific examples of "aryl which may be substituted" and "heteroaryl which may be substituted", there may be mentioned: dibenzofuranyl, naphthobenzofuranyl, phenyl-substituted dibenzofuranyl, and the like.
At least one hydrogen in the compound represented by formula (1) may be substituted with halogen, cyano, or deuterium. Examples of the "halogen" in the above case include: fluorine, chlorine, bromine, and iodine. Particularly preferred is a compound represented by the formula (3-H2) wherein all hydrogens are replaced with deuterium.
In the formula (3-H2), R c Is hydrogen, alkyl, or cycloalkyl, preferably hydrogen, methyl, or tert-butyl, more preferablyIs selected as hydrogen.
In the formula (3-H2), ar is preferred 11 ～Ar 18 At least two of (a) are aryl which may be substituted or heteroaryl which may be substituted. That is, the anthracene compound represented by the formula (3-H2) preferably has a structure in which at least three substituents selected from the group consisting of an aryl group which may be substituted and a heteroaryl group which may be substituted are bonded to an anthracene ring.
The anthracene compound represented by the formula (3-H2) is more preferably Ar 11 ～Ar 18 Two of (a) are aryl which may be substituted or heteroaryl which may be substituted, the other six are hydrogen, alkyl which may be substituted, cycloalkyl which may be substituted, alkenyl which may be substituted, or alkoxy which may be substituted. That is, the anthracene compound represented by the formula (3-H2) more preferably has a structure in which three substituents selected from the group consisting of an aryl group which may be substituted and a heteroaryl group which may be substituted are bonded to an anthracene ring.
The anthracene compound represented by the formula (3-H2) is more preferably Ar 11 ～Ar 18 Any two of which are optionally substituted aryl or optionally substituted heteroaryl, and the other six of which are hydrogen, methyl, or tert-butyl.
Further, R in the formula (3-H2) is preferably R c Is hydrogen and Ar 11 ～Ar 18 Any six of (a) are hydrogen.
The anthracene compound represented by the formula (3-H2) is preferably an anthracene compound represented by the following formula (3-H2-A), formula (3-H2-B), formula (3-H2-C), formula (3-H2-D), or formula (3-H2-E).
[ solution 78]
Figure BDA0003615335190000811
In the formula (3-H2-A), the formula (3-H2-B), the formula (3-H2-C), the formula (3-H2-D) or the formula (3-H2-E), ar c '、Ar 11 '、Ar 12 '、Ar 13 '、Ar 14 '、Ar 15 '、Ar 17 ', and Ar 18 ' independently represent a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a benzofluorenyl group, a,
Figure BDA0003615335190000822
A group, a triphenylene group, a pyrenyl group, or a group represented by the formula (A), at least one of these groups being hydrogen-substituted phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, fluorenyl,
Figure BDA0003615335190000823
A group represented by the formula (A). Here, when the hydrogens of the methylene groups in the fluorenyl and benzofluorenyl groups are substituted with phenyl groups, the phenyl groups may be bonded to each other by a single bond. Not bonding Ar c '、Ar 11 '、Ar 12 '、Ar 13 '、Ar 14 '、Ar 15 '、Ar 17 ', and Ar 18 Instead of hydrogen, the carbon atom of the anthracycline of' may be bonded with a methyl group or a tert-butyl group.
When Ar is c '、Ar 11 '、Ar 12 '、Ar 13 '、Ar 14 '、Ar 15 '、Ar 17 ', and Ar 18 ' when each is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, a group represented by any one of the formulae (3-H2-X1) to (3-H2-X7) is preferable.
Ar c '、Ar 11 '、Ar 12 '、Ar 13 '、Ar 14 '、Ar 15 '、Ar 17 ', and Ar 18 'more preferably each independently represents a phenyl group, a biphenyl group (particularly biphenyl-2-yl or biphenyl-4-yl), a terphenyl group (particularly m-terphenyl-5' -yl), a naphthyl group, a phenanthryl group, a fluorenyl group, or a group represented by any one of the formulae (a-1) to (a-4), in which case at least one of these groups may be substituted with a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, or a group represented by any one of the formulae (a-1) to (a-4).
In addition, at least one hydrogen of the compounds represented by formula (3-H2-A), formula (3-H2-B), formula (3-H2-C), formula (3-H2-D), or formula (3-H2-E) may be substituted with halogen, cyano, or deuterium. The form is preferably a deuterated form, and more preferably a form in which all of the anthracyclines are deuterated, or a form in which all of the hydrogen atoms are deuterated.
Particularly preferred anthracene compounds represented by the formula (3-H2) include anthracene compounds represented by the following formula (3-H2-Aa).
[ solution 79]
Figure BDA0003615335190000821
In the formula (3-H2-Aa), ar c '、Ar 14 ', and Ar 15 ' are each independently phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, or,
Figure BDA0003615335190000824
A triphenylene group, a pyrenyl group, or a group represented by any one of the formulae (A-1) to (A-11), at least one of these groups being hydrogen-substituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, fluorenyl,
Figure BDA0003615335190000825
A triphenylene group, a pyrenyl group, or a group represented by any one of the formulae (A-1) to (A-11). Here, when the hydrogens of the methylene groups in the fluorenyl and benzofluorenyl groups are substituted with phenyl groups, the phenyl groups may be bonded to each other by a single bond. In addition, ar is not bonded c '、Ar 14 ', and Ar 15 In place of hydrogen, the carbon atom of the anthracycline of' may be substituted with a methyl group or a tert-butyl group. At least one hydrogen in the compound represented by formula (3-H2-Aa) may be substituted with halogen or cyano, and at least one hydrogen in the compound represented by formula (3-H2-Aa) may be substituted with deuterium.
In the formula (3-H2-Aa), ar c '、Ar 14 ', and Ar 15 ' is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, or a group represented by any one of the formulae (a-1) to (a-4), and at least one hydrogen of these groups may be substituted by a phenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, or a group represented by any one of the formulae (a-1) to (a-4).
Among the compounds represented by the formula (3-H2-Aa), preferred isSelected from carbon (Ar) bonded to at least 10-position of anthracene ring c The carbon of the' bond is set to the 9-position) is substituted with deuterium. That is, the compound represented by the formula (3-H2-Aa) is preferably a compound represented by the following formula (3-H2-Ab). In addition, in the formula (3-H2-Ab), D is deuterium, ar c '、Ar 14 ', and Ar 15 ' is as defined in the formula (3-H2-Aa). D in the formula (3-H2-Ab) represents that at least the position is deuterium, any hydrogen or more than any other hydrogen in the formula (3-H2-Ab) is deuterium at the same time, and it is also preferable that all the hydrogens in the formula (3-H2-Ab) are deuterium.
[ solution 80]
Figure BDA0003615335190000831
Specific examples of the anthracene compound include compounds represented by the formulae (3-131-Y) to (3-182-Y), the formulae (3-183-N), the formulae (3-184-Y) to (3-284-Y), the formulae (3-500) to (3-557), the formulae (3-600) to (3-605), and the formulae (3-606-Y) to (3-626-Y). The hydrogen atoms in these formulae may be partially or completely substituted with deuterium, but the forms of deuterium substitution which are particularly preferred are listed individually. In which Y may be-O-, -S-, > N-R 29 (R 29 Is the same definition as described) or > C (-R) 30 ) 2 (R 30 Is an aryl group or an alkyl group which may be bonded), R 29 For example phenyl, R 30 For example methyl. With respect to the formula number, for example, in the case where Y is O, the formula (3-131-Y) is set to the formula (3-131-O), and in the case where Y is-S-or > N-R 29 In the case of (2), the formula (3-131-S) or the formula (3-131-N) is used, respectively.
[ solution 81]
Figure BDA0003615335190000841
[ solution 82]
Figure BDA0003615335190000851
[ solution 83]
Figure BDA0003615335190000861
[ chemical formula 84]
Figure BDA0003615335190000871
[ solution 85]
Figure BDA0003615335190000881
[ solution 86]
Figure BDA0003615335190000891
[ solution 87]
Figure BDA0003615335190000901
[ 88]
Figure BDA0003615335190000911
[ solution 89]
Figure BDA0003615335190000921
[ solution 90]
Figure BDA0003615335190000931
[ solution 91]
Figure BDA0003615335190000941
[ solution 92]
Figure BDA0003615335190000942
[ chemical No. 93]
Figure BDA0003615335190000951
[ chemical 94]
Figure BDA0003615335190000961
[ solution 95]
Figure BDA0003615335190000971
[ solution 96]
Figure BDA0003615335190000981
[ chemical 97]
Figure BDA0003615335190000991
[ solution 98]
Figure BDA0003615335190001001
[ solution 99]
Figure BDA0003615335190001011
[ solution 100]
Figure BDA0003615335190001021
In the formula, D is deuterium.
Among these compounds, preferred are the formula (3-131-Y) to the formula (3-134-Y), the formula (3-138-Y), the formula (3-140-Y) to the formula (3-143-Y), the formula (3-150-Y), the formula (3-153-Y) to the formula (3-156-Y), the formula (3-166-Y), the formula (3-168-Y), the formula (3-173-Y), the formula (3-177-Y), the formula (3-180-Y) to the formula (3-183-N), the formula (3-185-Y), the formula (3-190-Y), the formula (3-223-Y), the formula (3-241-Y), the formula (3-250-Y), the formula (3-252-Y) to the formula (3-254-Y), the formula (3-270-Y) to the formula (3-284-Y), the formula (3-501), the formula (3-507), the formula (3-508), the formula (3-509), the formula (3-514-547), the formula (3-521), the formula (3-538) or the formula (3-538) (3-605) and the formulae (3-606-Y) to (3-626-Y). In addition, Y is preferably-O-or > N-R 29 More preferably-O-. In addition, deuterium substitution is also preferred.
The anthracene compound may be a compound having a reactive group at a desired position of an anthracene skeleton as a starting material, and in the case of the anthracene compound represented by formula (3-H), the anthracene compound may be one having X and Ar 4 And a compound having a reactive group in a partial structure such as the structure of the formula (A) as a starting material, and produced by suzuki coupling, radial and shore coupling, or other known coupling reaction. Examples of the reactive group of these reactive compounds include halogen and boric acid. As a specific production method, for example, refer to paragraph [0089 ] of International publication No. 2014/141725]Paragraph [0175 ]]The synthesis method of (1).
< fluorene compound >
The compound represented by the formula (4-H) functions basically as a host.
[ solution 101]
Figure BDA0003615335190001031
In the formula (4-H),
R 1 to R 10 Each independently is hydrogen, aryl, heteroaryl (saidThe heteroaryl group may be bonded to the fluorene skeleton in the formula (4-H) via a linking group), a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an aryloxy group, at least one of which may be substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, and R 1 And R 2 、R 2 And R 3 、R 3 And R 4 、R 5 And R 6 、R 6 And R 7 、R 7 And R 8 Or R 9 And R 10 May be independently bonded to form a condensed ring or a spiro ring, at least one hydrogen in the formed ring may be substituted with an aryl group, a heteroaryl group (the heteroaryl group may be bonded to the formed ring via a linking group), a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an aryloxy group, at least one of these hydrogen may be substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, and at least one hydrogen in the compound represented by formula (4-H) may be substituted with halogen, cyano group, or deuterium.
The details of each group in the definition of the formula (4-H) can be cited in the description of the polycyclic aromatic compound of the formula (1).
As R 1 To R 10 Examples of the alkenyl group in (b) include alkenyl groups having 2 to 30 carbon atoms, preferably alkenyl groups having 2 to 20 carbon atoms, more preferably alkenyl groups having 2 to 10 carbon atoms, further preferably alkenyl groups having 2 to 6 carbon atoms, and particularly preferably alkenyl groups having 2 to 4 carbon atoms. Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.
Specific examples of the heteroaryl group include a monovalent group represented by a compound of the following formula (4-Ar 1), formula (4-Ar 2), formula (4-Ar 3), formula (4-Ar 4) or formula (4-Ar 5) from which any one hydrogen atom has been removed.
[ solution 102]
Figure BDA0003615335190001032
In the formulae (4-Ar 1) to (4-Ar 5), Y 1 Each independently is O, S or N-R, R is phenyl, biphenyl, naphthyl, anthracenyl or hydrogen, at least one hydrogen in the structures of formulae (4-Ar 1) to (4-Ar 5) may be substituted with phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.
These heteroaryl groups may be bonded to the fluorene skeleton in the formula (4-H) through a linking group. That is, the fluorene skeleton and the heteroaryl group in the formula (4-H) may be bonded not only directly but also via a linking group therebetween. Examples of the linking group include: phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH 2 CH 2 -、-CH 2 CH 2 O-, or-OCH 2 CH 2 O-, etc.
Further, R in the formula (4-H) 1 And R 2 、R 2 And R 3 、R 3 And R 4 、R 5 And R 6 、R 6 And R 7 Or R 7 And R 8 Each of which may independently be bonded to form a condensed ring, R 9 And R 10 May be bonded to form a spiro ring. From R 1 To R 8 The condensed ring to be formed is a ring condensed on the benzene ring in the formula (4-H), and is an aliphatic ring or an aromatic ring. An aromatic ring is preferable, and as a structure including a benzene ring in the formula (4-H), a naphthalene ring, a phenanthrene ring, or the like can be mentioned. From R 9 And R 10 The spiro ring to be formed is a ring spiro-bonded to the 5-membered ring in the formula (4-H), and is an aliphatic ring or an aromatic ring. Preferred is an aromatic ring, and fluorene rings and the like are exemplified.
The compound represented by the formula (4-H) is preferably a compound represented by the following formula (4-H-1), formula (4-H-2) or formula (4-H-3), and is R in the formula (4-H) 1 And R 2 A compound formed by condensation of bonded benzene rings, R in the formula (4-H) 3 And R 4 A compound formed by condensation of bonded benzene rings, R in the formula (4-H) 1 To R 8 Is not bonded.
[ solution 103]
Figure BDA0003615335190001041
R in the formula (4-H-1), the formula (4-H-2) and the formula (4-H-3) 1 To R 10 Is defined as R corresponding to formula (4-H) 1 To R 10 R in the same formulae (4-H-1) and (4-H-2) 11 To R 14 Is also defined as R in the formula (4-H) 1 To R 10 The same is true.
The compound represented by the formula (4-H) is more preferably a compound represented by the following formula (4-H-1A), formula (4-H-2A) or formula (4-H-3A), and is R in the formula (4-H-1), formula (4-H-2) or formula (4-H-3) 9 And R 10 A compound bonded to form a spiro-fluorene ring.
[ solution 104]
Figure BDA0003615335190001051
R in the formulae (4-H-1A), (4-H-2A) and (4-H-3A) 2 To R 7 Are defined as R corresponding to the formulae (4-1), (4-2) and (4-3) 2 To R 7 R in the same formulae (4-H-1A) and (4-H-2A) 11 To R 14 Is also defined as R in the formula (4-1) and the formula (4-2) 11 To R 14 The same is true.
Further, all or a part of hydrogen in the compound represented by the formula (4-H) may be substituted with halogen, cyano or deuterium.
More specific examples of the fluorene compound as a main body of the present invention include compounds represented by the following structural formulae. Further, "Me" represents a methyl group.
[ solution 105]
Figure BDA0003615335190001061
< dibenzo >
Figure BDA0003615335190001063
Compound (I)
Dibenzo as host
Figure BDA0003615335190001064
The compound is, for example, a compound represented by the following formula (5-H).
[ solution 106]
Figure BDA0003615335190001062
In the formula (5-H), R 1 To R 16 Independently of one another, hydrogen, aryl, heteroaryl (which may be bonded to the dibenzo of formula (5-H) via a linking group
Figure BDA0003615335190001072
Backbone bond), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, and R 1 To R 16 Wherein adjacent groups may be bonded to each other to form a condensed ring, at least one hydrogen in the formed ring may be substituted with an aryl group, a heteroaryl group (the heteroaryl group may be bonded to the formed ring via a linking group), a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an aryloxy group, at least one hydrogen of these may be substituted with an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, and at least one hydrogen in the compound represented by the formula (5-H) may be substituted with halogen, cyano group, or deuterium.
The details of each group in the definition of the formula (5-H) can be cited in the description of the polycyclic aromatic compound of the formula (1).
Examples of the alkenyl group in the definition of the formula (5-H) include alkenyl groups having 2 to 30 carbon atoms, preferably alkenyl groups having 2 to 20 carbon atoms, more preferably alkenyl groups having 2 to 10 carbon atoms, still more preferably alkenyl groups having 2 to 6 carbon atoms, and particularly preferably alkenyl groups having 2 to 4 carbon atoms. Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl.
Specific examples of the heteroaryl group include a monovalent group represented by a compound of the following formula (5-Ar 1), formula (5-Ar 2), formula (5-Ar 3), formula (5-Ar 4) or formula (5-Ar 5) except for any one hydrogen atom.
[ solution 107]
Figure BDA0003615335190001071
In the formulae (5-Ar 1) to (5-Ar 5), Y 1 Each independently is O, S or N-R, R is phenyl, biphenyl, naphthyl, anthracenyl or hydrogen, at least one hydrogen in the structures of formula (5-Ar 1) to (5-Ar 5) may be substituted with phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, methyl, ethyl, propyl, or butyl.
These heteroaryl groups may be bonded to the dibenzo of formula (5-H) via a linking group
Figure BDA0003615335190001073
Backbone bonding. Namely, dibenzo in the formula (5-H)
Figure BDA0003615335190001074
The backbone and the heteroaryl group may be bonded not only directly but also via a linking group between these. Examples of the linking group include: phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH 2 CH 2 -、-CH 2 CH 2 O-, or-OCH 2 CH 2 O-, etc.
The compound represented by the formula (5-H) is preferably R 1 、R 4 、R 5 、R 8 、R 9 、R 12 、R 13 And R 16 Is hydrogen. In the case, R in the formula (5-H) 2 、R 3 、R 6 、R 7 、R 10 、R 11 、R 14 And R 15 Preferably hydrogen, phenyl, biphenyl, naphthyl and anthraceneA radical, a phenanthryl radical, a monovalent radical having the structure of formula (5-Ar 1), formula (5-Ar 2), formula (5-Ar 3), formula (5-Ar 4) or formula (5-Ar 5) (the monovalent radical having the structure may be substituted by phenylene, biphenylene, naphthylene, anthracylene, methylene, ethylene, -OCH 2 CH 2 -、-CH 2 CH 2 O-, or-OCH 2 CH 2 O-and dibenzo of formula (5-H)
Figure BDA0003615335190001075
Backbone bond), methyl, ethyl, propyl, or butyl.
The compound represented by the formula (5-H) is more preferably R 1 、R 2 、R 4 、R 5 、R 7 、R 8 、R 9 、R 10 、R 12 、R 13 、R 15 And R 16 Is hydrogen. In the case where R in the formula (5-H) 3 、R 6 、R 11 And R 14 Is a single bond via phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH 2 CH 2 -、-CH 2 CH 2 O-, or-OCH 2 CH 2 O-is a monovalent group having a structure of formula (5-Ar 1), formula (5-Ar 2), formula (5-Ar 3), formula (5-Ar 4) or formula (5-Ar 5), at least one other than (i.e., other than the position where the monovalent group having the structure is substituted) is hydrogen, phenyl, biphenyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl, and at least one hydrogen of these may be substituted by phenyl, biphenyl, naphthyl, anthracenyl, methyl, ethyl, propyl, or butyl.
In addition, R in the formula (5-H) 2 、R 3 、R 6 、R 7 、R 10 、R 11 、R 14 And R 15 In the case of selecting a monovalent group having a structure represented by formula (5-Ar 1) to formula (5-Ar 5), at least one hydrogen in the structure may react with R in formula (5-H) 1 To R 16 Any of which is bonded to form a single bond.
The dibenzo compounds of the present invention
Figure BDA0003615335190001082
More specific examples of the compound include compounds represented by the following structural formulae. Further, "tBu" represents a tert-butyl group.
[ solution 108]
Figure BDA0003615335190001081
[ chemical 109]
Figure BDA0003615335190001091
The material for the light-emitting layer (host material and dopant material) may be used as a polymer compound obtained by polymerizing a reactive compound obtained by substituting a reactive substituent in the material for the light-emitting layer (host material and dopant material) as a monomer, or a crosslinked polymer thereof obtained by reacting a main chain polymer with the reactive compound, or a pendant polymer compound obtained by substituting a reactive substituent in the material for the light-emitting layer (host material and dopant material) or a crosslinked pendant polymer thereof. As the reactive substituent in the above case, the description of the polycyclic aromatic compound represented by the formula (1) can be cited.
Luminescent layer containing auxiliary dopant and emission dopant
A light-emitting layer in an organic electroluminescent element may contain a host compound as a first component, an auxiliary dopant (compound) as a second component, and an emitting dopant (compound) as a third component. The polycyclic aromatic compounds of the invention are also preferably used as emissive dopants. As the auxiliary dopant (compound), a thermally active type retardation phosphor can be used.
In the following description, an organic electroluminescent element using a thermally active delayed phosphor as an auxiliary dopant is sometimes referred to as a "TAF element" (thermally active delayed Fluorescence (TADF) assisted Fluorescence (assisted Fluorescence) element). The "host compound" in the TAF device is a compound having a lower minimum excited singlet level determined from a shoulder on the short wavelength side of the peak of the fluorescence spectrum than the thermally active retardation phosphor as the second component and the emission dopant as the third component.
The "thermally active type delayed phosphor" refers to a compound that absorbs thermal energy, generates reverse intersystem crossing from a lowest excited triplet state to a lowest excited singlet state, and is radioactively inactivated from the lowest excited singlet state, thereby being capable of radioactively delaying fluorescence. Here, the "thermally active delayed fluorescence" also includes a case where a higher-order triplet state passes through in an excitation process from a lowest excited triplet state to a lowest excited singlet state. For example, there may be cited papers published by munkman et al of the university of Durham (Durham) (naturecomms), 7. In the present invention, regarding a sample containing a target compound, the target compound is determined to be a "thermally active type delayed phosphor" on the basis of the observation of a slow fluorescence component when the fluorescence lifetime is measured at 300K. The slow fluorescence component herein refers to a component having a fluorescence lifetime of 0.1 μ sec or more. The fluorescence lifetime can be measured, for example, using a fluorescence lifetime measuring apparatus (manufactured by Hamamatsu Photonics, inc., C11367-01).
The polycyclic aromatic compound of the present invention can function as an emitting dopant, and the "thermally active delayed phosphor" can function as an auxiliary dopant for assisting the luminescence of the polycyclic aromatic compound of the present invention.
Fig. 2 is a diagram showing an energy level of a light-emitting layer of a TAF element using a general fluorescent dopant for an Emitting Dopant (ED). In the figure, the Energy level of the ground state of the host is E (1, G), the lowest excited singlet state Energy level of the host determined from the shoulder on the short-wavelength side of the Fluorescence spectrum is E (1, S, sh), the lowest excited triplet state Energy level of the host determined from the shoulder on the short-wavelength side of the phosphorescence spectrum is E (1, T, sh), the Energy level of the ground state of the auxiliary dopant as the second component is E (2, G), the lowest excited singlet state Energy level of the auxiliary dopant as the second component determined from the shoulder on the short-wavelength side of the Fluorescence spectrum is E (2, S, sh), the lowest excited triplet level obtained from the shoulder at the short wavelength side of the phosphorescence spectrum of the auxiliary dopant as the second component is E (2,t, sh), the ground level of the emitting dopant as the third component is E (3,g), the lowest excited singlet level obtained from the shoulder at the short wavelength side of the Fluorescence spectrum of the emitting dopant as the third component is E (3,s, sh), the lowest excited triplet level obtained from the shoulder at the short wavelength side of the phosphorescence spectrum of the emitting dopant as the third component is E (3,t, sh), the hole is h +, the electron is E-, and the Fluorescence Resonance Energy Transfer is FRET (Fluorescence Resonance Energy Transfer). In the TAF element, when a general fluorescent dopant is used as the Emitting Dopant (ED), the energy of Up-Conversion (Up Conversion) from the auxiliary dopant is transferred to the lowest excited singlet level E (3, s, sh) of the emitting dopant and light is emitted. However, a portion of the lowest excited triplet level E (2, t, sh) on the auxiliary dopant moves to the lowest excited triplet level E (3, t, sh) of the emitting dopant, or intersystem crossing from the lowest excited singlet level E (3, s, sh) to the lowest excited triplet level E (3, t, sh) occurs on the emitting dopant, followed by thermal deactivation to the ground state E (3, g). Due to the path, a part of the energy is not used for emitting light, and waste of energy occurs.
In contrast, in the organic electroluminescent element of the present embodiment, energy efficiency in moving from the auxiliary dopant to the emitting dopant can be used for light emission, and thus high light emission efficiency can be achieved. This is presumably caused by the following light emission mechanism.
Fig. 3 shows a preferable energy relationship in the organic electroluminescent element of this embodiment. In the organic electroluminescent element of this embodiment, the compound having a boron atom as an emission dopant has a high lowest excited triplet level E (3,t, sh). Therefore, in the case where the excited singlet energy up-converted by the auxiliary dopant is intersystem crossing to the lowest excited triplet level E (3,t, sh), for example, by the emitting dopant, the lowest excited triplet level E (2,t, sh) on the auxiliary dopant (thermally active type delayed phosphor) is also up-converted or recovered on the emitting dopant. Therefore, the generated excitation energy can be used for light emission without waste. In addition, it is expected that by assigning the functions of up-conversion and luminescence to two kinds of molecules whose respective functions are highlighted, the retention time of high energy is reduced, and the load on the compound is reduced.
In this embodiment, a known compound can be used as the host compound, and examples thereof include a compound having at least one of a carbazole ring and a furan ring, and among them, a compound in which at least one of a furyl group and a carbazole group and at least one of an arylene group and a heteroarylene group are bonded is preferably used. Specific examples thereof include mCP and mCBP.
From the viewpoint of promoting but not inhibiting the generation of TADF in the light-emitting layer, the lowest excited triplet level E (1, t, sh) of the host compound, which is determined from a shoulder on the short wavelength side of the peak of the phosphorescence spectrum, is preferably higher than the lowest excited triplet levels E (2, t, sh) and E (3, t, sh) of the emissive dopant or the assist dopant having the highest lowest excited triplet level in the light-emitting layer, and specifically, the lowest excited triplet level E (1, t, sh) of the host compound is preferably 0.01eV or more, more preferably 0.03eV or more, and still more preferably 0.1eV or more, as compared with E (2, t, sh) and E (3, t, sh). In addition, a compound having TADF activity may also be used as the host compound.
As the host compound, for example, a compound represented by any of the above-described formulae (H1), (H2), and (H3) can be used.
< thermally active type delayed phosphor (auxiliary dopant) >)
The thermally active retardation phosphor (TADF compound) used in the TAF element is preferably a donor-acceptor type thermally active retardation phosphor (D-a type TADF compound) as follows: it is designed to localize the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) within a molecule using an electron donating substituent called donor and an electron accepting substituent called acceptor to produce efficient reverse interbody crossing. In the present specification, the term "electron donating substituent" (donor) refers to a substituent and a partial structure that are localized in the HOMO orbital of the molecule of the thermally active retardation phosphor, and the term "electron accepting substituent" (acceptor) refers to a substituent and a partial structure that are localized in the LUMO orbital of the molecule of the thermally active retardation phosphor.
Generally, a thermally active retardation phosphor using a donor or acceptor has a large Spin Orbit Coupling (SOC) due to the structure, a small exchange interaction between HOMO and LUMO, and a small Δ E (ST), and thus can obtain a very fast reverse intersystem crossing rate. On the other hand, a thermally active type delayed phosphor using a donor or an acceptor has a large structural relaxation in an excited state (in a molecule, since a stable structure is different between a ground state and an excited state, when a transition from the ground state to the excited state occurs by an external stimulus, the structure is changed to the stable structure in the excited state thereafter), and provides a wide emission spectrum, and thus when used as a light emitting material, there is a possibility that color purity may be lowered.
As the thermally active type retardation phosphor in the TAF device, for example, a compound in which a donor and an acceptor are bonded directly or via a spacer can be used. Examples of the electron donating group (donor structure) and the electron accepting group (acceptor structure) used in the thermally active retardation phosphor of the present invention include structures described in "Materials Chemistry of Materials", 2017,29, 1946-1963. Examples of the structure of the applicator include: carbazole, dimethylcarbazole, di-t-butylcarbazole, dimethoxycarbazole, tetramethylcarbazole, benzofluorocarbazole, benzothienocarbazole, phenylindolinocarbazole, phenylbicarbazole, bicarbazole, terparbazole, diphenylcarbazylamine, tetraphenylcarbazolyldiamine, phenoxazine, dihydrophenazine, phenothiazine, dimethylacridine, diphenylamine, bis (t-butylphenyl) amine, N1- (4- (diphenylamino) phenyl) -N4, N4-diphenylbenzene-1, 4-diamine, dimethylatetraphenyldihydroacridine diamine, tetramethyl-dihydro-indenyl acridine, and diphenyl-dihydrodibenzoazacillin. Examples of acceptor structures include: sulfonyl-diphenyl, benzophenone, phenylenebis (phenyl ketone), benzonitrile, isonicotinic nitrile, phthalonitrile, isophthalonitrile, parachlorophthalonitrile, benzenetricarboxylic nitrile, triazole, oxazole, thiadiazole, benzothiazole, benzobis (thiazole), benzoxazole, benzobis (oxazole), quinoline, benzimidazole, dibenzoquinoxaline, heptaazaphenalene, thioxanthone dioxide, dimethyl anthrone, anthracenedione, 5H-cyclopenta [1,2-b:5,4-b' ] bipyridinyl, fluorenyldicarbonitrile, triphenyltriazine, pyrazinedicarboxyanide, pyrimidine, phenylpyrimidine, methylpyrimidine, pyridinedicarbonitrile, dibenzoquinoxaline dicarbonitrile, bis (phenylsulfonyl) benzene, dimethylthioxanthene dioxide, thianthrene tetraoxide, tris (dimethylphenyl) borane, and the like. In particular, the compound having thermally active delayed fluorescence in the TAF element is preferably a compound having at least one partial structure selected from carbazole, phenoxazine, acridine, triazine, pyrimidine, pyrazine, thioxanthene, benzonitrile, phthalonitrile, isophthalonitrile, diphenylsulfone, triazole, oxadiazole, thiadiazole, and benzophenone.
The compound serving as the second component of the light-emitting layer in the TAF device is a thermally active retardation phosphor, and is preferably a compound whose emission spectrum overlaps at least a part of the absorption peak of the emitting dopant. Hereinafter, compounds useful as a second component (thermally active type retardation phosphors) of a light-emitting layer in a TAF device are exemplified. The compounds that can be used as the thermally active retardation phosphors in the TAF element are not to be construed as being limited to the following exemplified compounds. In the following formula, me represents a methyl group, tBu represents a t-butyl group, and the wavy line represents a bonding site.
[ solution 110]
Figure BDA0003615335190001131
[ solution 111]
Figure BDA0003615335190001141
[ chemical 112]
Figure BDA0003615335190001151
[ solution 113]
Figure BDA0003615335190001161
[ chemical formula 114]
Figure BDA0003615335190001162
Further, as the thermally active retardation phosphor, a compound represented by any one of the following formulae (AD 1), (AD 2), and (AD 3) may be used.
[ solution 115]
Figure BDA0003615335190001171
In the formulas (AD 1), (AD 2) and (AD 3), M is respectively and independently a single bond, -O-, > N-Ar or > CAr 2 From the viewpoint of the depth of HOMO of the partial structure to be formed and the heights of the lowest excited singlet level and the lowest excited triplet level, a single bond, -O-, or > N-Ar is preferable. J is toThe donor-side structure and the acceptor-side structure are each independently an arylene group having 6 to 18 carbon atoms, and preferably an arylene group having 6 to 12 carbon atoms from the viewpoint of the size of the conjugate exuded from the donor-side structure and the acceptor-side structure. More specifically, there may be mentioned: phenylene, methylphenylene and dimethylphenylene. Q is independently = C (-H) -or = N-, and is preferably = N-from the viewpoint of the shallowness of the LUMO of the partial structure formed and the heights of the lowest excited singlet level and the lowest excited triplet level. Ar is independently hydrogen, an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 18 carbon atoms, and from the viewpoints of the depth of the HOMO of the partial structure to be formed and the heights of the lowest excited singlet level and the lowest excited triplet level, it is preferably hydrogen, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 14 carbon atoms, an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 6 to 10 carbon atoms, more preferably hydrogen, phenyl, tolyl, xylyl, mesitylphenyl, biphenyl, pyridyl, bipyridyl, triazinyl, carbazolyl, dimethylcarbazolyl, di-tert-butylcarbazolyl, benzimidazolyl or phenylbenzimidazolyl, and further preferably hydrogen, phenyl or carbazolyl. m is 1 or 2.n is an integer of not more than (6-m), and is preferably an integer of 4 to (6-m) from the viewpoint of steric hindrance. Further, at least one hydrogen in the compounds represented by each of the formulae may be substituted with halogen or deuterium.
More specifically, the compound used as the second component in this form is preferably 4CzBN, 4CzBN-Ph, 5CzBN, 3Cz2DPhCzBN, 4CzIPN, 2PXZ-TAZ, cz-TRZ3, BDPCC-TPTA, MA-TA, PA-TA, FA-TA, PXZ-TRZ, DMAC-TRZ, BCzT, DCzTrz, DDCzTRz, spiro AC-TRZ, ac-HPM, ac-PPM, ac-MPM, TCzTrz, tmCzTrz and DCzmCZTrz.
The compound used as the second component in this embodiment may be a donor-acceptor type TADF compound represented by D-a in which one donor D is directly bonded to one acceptor a or bonded through a linking group, and a compound having a structure represented by the following formula (DAD 1) in which a plurality of donors D are directly bonded or bonded to one acceptor a through a linking group is preferable because it is a compound having more excellent characteristics of an organic electroluminescent element.
(D 1 -L 1 )n-A 1 (DAD1)
The formula (DAD 1) includes a compound represented by the following formula (DAD 2).
D 2 -L 2 -A 2 -L 3 -D 3 (DAD2)
In the formulae (DAD 1) and (DAD 2), D 1 、D 2 And D 3 Each independently represents a donor group. As the donor group, a structure of the donor can be employed. A. The 1 And A 2 Each independently represents a receptor group. As the acceptor group, a structure of the acceptor can be used. L is 1 、L 2 And L 3 Each independently represents a single bond or a conjugated linking group. The conjugated linking group has a spacer structure for separating the donor group and the acceptor group, and is preferably an arylene group having 6 to 18 carbon atoms, and more preferably an arylene group having 6 to 12 carbon atoms. L is 1 、L 2 And L 3 More preferably, each is independently phenylene, methylphenylene or dimethylphenylene. N in the formula (DAD 1) is more than 2 and represents A 1 An integer of not more than the maximum number of substitutents that can be performed. n may be selected, for example, in the range of 2 to 10, or in the range of 2 to 6. When n is 2, it is a compound represented by the formula (DAD 2). n number of D 1 N, which may be the same or different, L 1 May be the same or different. Preferred specific examples of the compounds represented by the formula (DAD 1) and the formula (DAD 2) include 2PXZ-TAZ and the following compounds, and the second component usable in the present invention is not limited to these compounds.
[ solution 116]
Figure BDA0003615335190001191
In this embodiment, the light-emitting layer may be a single layer or may include a plurality of layers. The host compound, the thermally active delayed phosphor, and the polycyclic aromatic compound of the present invention may be contained in the same layer, or at least one component may be contained in each of a plurality of layers. The host compound, the thermally active retardation phosphor, and the polycyclic aromatic compound of the present invention contained in the light-emitting layer may be one kind or a combination of plural kinds. The assistant dopant and the emission dopant may be included in the bulk of the host compound as a host, or may be included in a portion of the host compound as a host. The light emitting layer doped with the assist dopant and the emission dopant may be formed by: a method of forming a film of a host compound, an auxiliary dopant and an emission dopant by a ternary co-evaporation method; a method in which a host compound, an auxiliary dopant and an emission dopant are mixed in advance and then simultaneously vapor-deposited; and a wet film-forming method for applying a composition (coating material) for forming a light-emitting layer, which is prepared by dissolving a host compound, an auxiliary dopant, and an emission dopant in an organic solvent.
The amount of the host compound to be used varies depending on the kind of the host compound, and may be determined by matching the characteristics of the host compound. The amount of the host compound used is preferably 40 to 99.999 mass%, more preferably 50 to 99.99 mass%, and still more preferably 60 to 99.9 mass%, based on the total mass of the light-emitting layer material. If in this range, it is preferable, for example, in terms of efficient charge transport and efficient energy movement toward the dopant.
The amount of the auxiliary dopant (thermally active retardation phosphor) used varies depending on the kind of the auxiliary dopant, and may be determined by the characteristics of the auxiliary dopant. The amount of the auxiliary dopant used is preferably 1 to 60 mass%, more preferably 2 to 50 mass%, and still more preferably 5 to 30 mass% of the total material for the light-emitting layer. The above range is preferable, for example, in terms of efficiently transferring energy to the emitting dopant.
The amount of the emitting dopant (compound having a boron atom) to be used differs depending on the kind of the emitting dopant, and may be determined by matching the characteristics of the emitting dopant. The amount of the emitting dopant used is preferably 0.001 to 30 mass%, more preferably 0.01 to 20 mass%, and still more preferably 0.1 to 10 mass% of the total material for the light-emitting layer. The above range is preferable, for example, in terms of preventing the concentration quenching phenomenon.
In terms of preventing the concentration quenching phenomenon, it is preferable that the amount of the emitting dopant used be low. In terms of the efficiency of the thermally active delayed fluorescence mechanism, it is preferable that the amount of the auxiliary dopant used be high. Further, in terms of the efficiency of the thermally active delayed fluorescence mechanism of the auxiliary dopant, it is preferable that the amount of the emitting dopant used is lower than the amount of the auxiliary dopant used.
< 2-1-3. Substrate in organic electroluminescent element
The substrate 101 is a support of the organic EL element 100, and quartz, glass, metal, plastic, or the like is generally used. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape according to the purpose, and for example, a glass plate, a metal foil, a plastic film, a plastic sheet, or the like can be used. Among them, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate and polysulfone are preferable. In the case of a glass substrate, soda-lime glass, alkali-free glass, or the like can be used, and the thickness is sufficient to maintain mechanical strength, and therefore, for example, 0.2mm or more is sufficient. The upper limit of the thickness is, for example, 2mm or less, preferably 1mm or less. The material of the glass is preferably alkali-free glass because it is preferable that the amount of eluted ions from the glass is small, and SiO is added 2 Etc. of barrier coating (barrier coat) are also commercially available, and therefore the soda-lime glass can be used. In order to improve the gas barrier property, a gas barrier film such as a fine silicon oxide film may be provided on at least one surface of the substrate 101, and particularly, when a synthetic resin plate, film or sheet having low gas barrier property is used as the substrate 101, it is preferable to provide a gas barrier film.
< 2-1-4. Anode in organic electroluminescent element
The anode 102 functions to inject holes into the light-emitting layer 105. When any one of the hole injection layer 103 and the hole transport layer 104 is provided between the anode 102 and the light-emitting layer 105, holes are injected into the light-emitting layer 105 through these layers.
As a material for forming the anode 102, an inorganic compound and an organic compound can be cited. Examples of the inorganic compound include: metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (Indium Oxide, tin Oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, or NESA glass, etc. Examples of the organic compound include: polythiophene such as poly (3-methylthiophene), and conductive polymer such as polypyrrole and polyaniline. Further, the organic EL element can be used by appropriately selecting from materials used as an anode of the organic EL element.
The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light-emitting element, but is preferably low in terms of power consumption of the light-emitting element. For example, an ITO substrate of 300 Ω/γ or less functions as an element electrode, but may be currently supplied to a substrate of about 10 Ω/γ, and therefore, it is particularly preferable to use a low-resistance product of, for example, 100 Ω/γ to 5 Ω/γ, and preferably 50 Ω/γ to 5 Ω/γ. The thickness of ITO can be arbitrarily selected depending on the resistance value, but is usually used in a range of 50nm to 300nm in many cases.
< 2-1-5 > hole injection layer, hole transport layer in organic electroluminescent element
The hole injection layer 103 functions to efficiently inject holes transferred from the anode 102 into the light-emitting layer 105 or the hole transport layer 104. The hole transport layer 104 functions to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light-emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are formed by laminating and mixing one or two or more kinds of hole injection/transport materials, or are formed by mixing a hole injection/transport material and a polymer binder. Further, an inorganic salt such as iron (III) chloride may be added to the hole injecting/transporting material to form a layer.
The hole injecting/transporting substance needs to efficiently inject/transport holes from the positive electrode between electrodes to which an electric field is applied, and it is desirable that the hole injecting efficiency is high and the injected holes are efficiently transported. Therefore, a substance having a small ionization potential, a large hole mobility, and excellent stability, and in which impurities serving as traps are not easily generated during production and use, is preferable.
As the material for forming the hole injection layer 103 and the hole transport layer 104, any compound can be selected from compounds conventionally used as charge transport materials for holes in photoconductive materials, p-type semiconductors, and known compounds used in hole injection layers and hole transport layers of organic EL devices. Specific examples of these compounds include carbazole derivatives (e.g., N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) and bis (N-alkylcarbazole), triarylamine derivatives (e.g., 4 '-tris (N-carbazolyl) triphenylamine, polymers having an aromatic tertiary amino group in the main chain or side chain, 1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N' -diphenyl-N, N '-di (3-methylphenyl) -4,4' -diaminobiphenyl, N '-diphenyl-N, N' -dinaphthyl-4, 4 '-diaminobiphenyl, N' -diphenyl-N, N '-di (3-methylphenyl) -4,4' -diphenyl-1, 1 '-diamine, N' -dinaphthyl-N, N '-diphenyl-4, 4' -diphenyl-1, 1 '-diamine, N' -diphenyl-N, N '-di (3-methylphenyl) -4,4' -diaminobiphenyl 4 ,N 4 ' -Diphenyl-N 4 ,N 4 '-bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]4,4' -diamine, N 4 ,N 4 ,N 4 ',N 4 '-tetrakis ([ 1,1' -biphenyl)]-4-yl) - [1,1' -biphenyl]Triphenylamine derivatives such as-4, 4 '-diamine, 4' -tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone-based compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9, 12-hexaazatriphenylene-2, 3,6,7,10, 11-hexachloronitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate or styrene derivative, polyvinylcarbazole, polysilane, and the like having the monomer in the side chain are preferable, but the polymer system may be used alone or in combination as long as it is a film necessary for the production of a light-emitting elementThe compound which can inject holes and further transport holes into the anode is not particularly limited.
Further, it is also known that the conductivity of an organic semiconductor is strongly affected by doping. Such an organic semiconductor matrix material contains a compound having a good electron donating property or a compound having a good electron accepting property. For doping electron-donating substances, strong electron acceptors such as Tetracyanoquinodimethane (TCNQ) and 2,3,5, 6-tetrafluorotetracyanoquinodimethane-1, 4-benzoquinodimethane (2, 3,5, 6-tetrafluorotetracyanodimethane-1, 4-benzoquinodimethane, F4 TCNQ) are known (for example, see documents "m. Faefer, a. Bayer, t. Friez, k. Rior (m. Pfeiffer, beyer, t.fritz, k.leo)," appl.phys.lett., "73 (22), 3202-3204 (1998)" and "j. Blohoverz,", m. Faisfet, t. Floritz, k. Rio (j. Blochwitz, m.pfeiffer, t.fritz, k.leo), "appl.phys.lett.," 73 (6), 729-731 (1998) ") are used. These generate so-called holes by an electron transfer process in an electron-donating base substance (hole-transporting substance). The conductivity of the base material varies considerably depending on the number and mobility of holes. As a matrix material having a hole transporting property, for example, a benzidine derivative (N, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) benzidine (TPD), etc.) or a starburst amine derivative (4,4 ',4 ″ -tris (N, N-diphenylamino) triphenylamine, TDATA, etc.), or a specific metal phthalocyanine (particularly zinc phthalocyanine (ZnPc), etc.) is known (japanese patent laid-open publication No. 2005-167175). The polycyclic aromatic compound of the present invention can be used as a material for forming a hole injection layer or a material for forming a hole transport layer.
< 2-1-6. Electron Barrier layer in organic electroluminescent element
An electron blocking layer for preventing diffusion of electrons from the light-emitting layer may be provided between the hole injection/transport layer and the light-emitting layer. The electron blocking layer may be formed using a compound represented by any one of the formulae (H1), (H2), and (H3). The polycyclic aromatic compound of the present invention is useful as a material for forming an electron blocking layer.
< 2-1-7. Electron injection layer, electron transport layer in organic electroluminescent element
The electron injection layer 107 functions to efficiently inject electrons transferred from the cathode 108 into the light-emitting layer 105 or the electron transport layer 106. The electron transport layer 106 functions to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transporting layer 106 and the electron injecting layer 107 are formed by laminating and mixing one or more kinds of electron transporting/injecting materials, or are formed by mixing an electron transporting/injecting material and a polymer binder.
The electron injection/transport layer is a layer that is responsible for injecting electrons from the cathode and transporting the electrons, and is preferably a layer that has high electron injection efficiency and transports the injected electrons with good efficiency. Therefore, a substance having a high electron affinity, a high electron mobility, and excellent stability is preferable, and impurities that become traps are less likely to be generated during production and use. However, when the balance between the transport of holes and electrons is considered, if the effect of efficiently blocking the flow of holes from the anode to the cathode side without being recombined is mainly exerted, the effect of improving the light emission efficiency is obtained as in the case of a material having a high electron transport ability even if the electron transport ability is not so high. Therefore, the electron injection/transport layer in this embodiment mode may also function as a layer that can efficiently block the transfer of holes.
The material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107 can be selected and used as desired from compounds conventionally used as electron transport compounds in photoconductive materials, and known compounds used in electron injection layers and electron transport layers of organic EL devices.
The material used for the electron transport layer or the electron injection layer preferably contains at least one compound selected from the following compounds: a compound containing an aromatic ring or a heteroaromatic ring containing at least one atom selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus; pyrrole derivatives and condensed ring derivatives thereof; and a metal complex having electron-accepting nitrogen. Specifically, there may be mentioned: aromatic ring derivatives having condensed ring systems such as naphthalene and anthracene, styrene-based aromatic ring derivatives represented by 4,4' -bis (diphenylvinyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphine oxide derivatives, arylnitrile derivatives, and indole derivatives. Examples of the metal complex having electron-accepting nitrogen include: and hydroxyoxazole complexes such as hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials may be used alone or in admixture with different materials.
Specific examples of the other electron transport compound include: pyridine derivatives, naphthalene derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (1, 3-bis [ (4-tert-butylphenyl) 1,3, 4-oxadiazolyl ] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2, 5-diphenyl-1, 3, 4-triazole, etc.), thiadiazole derivatives, metal complexes of 8-hydroxyquinoline (oxine) derivatives, hydroxyquinoline-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, indole (benzazole) compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2, 2' -bis (benzo [ h ] quinolin-2-yl) -9,9' -spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris (N-phenylbenzimidazole-2-yl) derivatives, benzene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, 4' -bis (1, 4' -triphenylpyridine-terphenyl) -2-yl) derivatives, 3, 4' -terpyridine derivatives, 3 ' -terpyridine derivatives, etc.), etc., pyridine derivatives, 4' -terpyridyl-2, 4' -naphthalene-2, 4' -triphenylpyridine derivatives, etc.) Aldazine derivatives, pyrimidine derivatives, arylnitrile derivatives, indole derivatives, phosphine oxide derivatives, bisstyryl derivatives, silole derivatives, oxazoline derivatives, and the like.
In addition, a metal complex having electron-accepting nitrogen may also be used, and examples thereof include: hydroxyoxazole complexes such as hydroxyquinoline metal complexes and hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes.
The materials can be used alone or in admixture with different materials.
Among the above materials, preferred are borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, arylnitrile derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, hydroxyquinoline-based metal complexes, thiazole derivatives, benzothiazole derivatives, silole derivatives, and oxazoline derivatives.
The polycyclic aromatic compound of the present invention can also be used as a material for forming an electron injection layer or a material for forming an electron transport layer.
The electron transport layer or the electron injection layer may further contain a substance capable of reducing a material forming the electron transport layer or the electron injection layer. As the reducing substance, various substances can be used as long as the substance has a certain reducing property, and for example, at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals can be preferably used.
Preferable reducing substances include alkali metals such as Na (work function 2.36 eV), K (work function 2.28 eV), rb (work function 2.16 eV), and Cs (work function 1.95 eV), and alkaline earth metals such as Ca (work function 2.9 eV), sr (work function 2.0 to 2.5 eV), and Ba (work function 2.52 eV), and particularly preferable substances have a work function of 2.9eV or less. Among these, the reducing substance is more preferably K, rb or Cs as an alkali metal, further preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing power, and by adding a relatively small amount of the alkali metals to a material forming the electron transporting layer or the electron injecting layer, improvement in light emission luminance or prolongation in life in the organic EL element can be achieved. In addition, as the reducing substance having a work function of 2.9eV or less, a combination of two or more of these alkali metals is also preferable, and a combination including Cs, for example, a combination of Cs and Na, cs and K, cs and Rb, or Cs and Na and K is particularly preferable. By including Cs, the reduction ability can be efficiently exerted, and by adding Cs to a material for forming an electron transport layer or an electron injection layer, improvement in light emission luminance or prolongation in life of an organic EL element can be achieved.
< 2-1-8. Cathode in organic electroluminescent element
The cathode 108 functions to inject electrons into the light-emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.
The material forming the cathode 108 is not particularly limited as long as it is a material capable of efficiently injecting electrons into the organic layer, and the same material as the material forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium, and magnesium, and alloys thereof (e.g., magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys such as lithium fluoride and aluminum) are preferable. In order to improve the electron injection efficiency to improve the element characteristics, lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy containing these low work function metals is effective. However, in general, these low work function metals are most often unstable in the atmosphere. In order to improve this, for example, a method of doping a minute amount of lithium, cesium, or magnesium into an organic layer and using an electrode having high stability is known. As the other dopant, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, the present invention is not limited to these examples.
Further, the following are preferable examples: metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, alloys using these metals, inorganic substances such as silicon dioxide, titanium dioxide, and silicon nitride, polyvinyl alcohol, vinyl chloride, and hydrocarbon-based polymer compounds are laminated to protect the electrodes. The method of manufacturing these electrodes is not particularly limited as long as conduction can be achieved by resistance heating, electron beam evaporation, sputtering, ion plating, coating, or the like.
< 2-1-9 > Binders usable in the layers
The materials used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer may be used individually or may be dispersed in a solvent-soluble resin such as polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene ether, polybutadiene, a hydrocarbon resin, a ketone resin, a phenoxy resin, polyamide, ethyl cellulose, a vinyl acetate resin, an acrylonitrile-butadiene-styrene (ABS) resin, or a polyurethane resin, or a curable resin such as a phenol resin, a xylene resin, a petroleum resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin, which is a polymer binder.
< 2-1-10. Method for manufacturing organic electroluminescent element
Each layer constituting the organic EL element can be formed by forming a material constituting each layer into a thin film by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, printing, ink jet, spin coating, casting, or coating. The film thickness of each layer formed in the above-described manner is not particularly limited, and may be appropriately set depending on the properties of the material, but is generally in the range of 2nm to 5000 nm. The film thickness can be measured by a crystal oscillation film thickness measuring apparatus or the like. When a thin film is formed by a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and the associated structure of the film, and the like. The deposition conditions are preferably set to +50 ℃ to +400 ℃ in a boat heating temperature and 10 degrees of vacuum -6 Pa～10 -3 Pa, deposition rate of 0.01 to 50nm/sec, substrate temperature of-15The temperature is suitably set in the range of 0 ℃ to +300 ℃ and the film thickness is suitably set in the range of 2nm to 5 μm.
Next, as an example of a method for manufacturing an organic EL element, a method for manufacturing an organic EL element including an anode, a hole injection layer, a hole transport layer, a light-emitting layer including a host material and a dopant material, an electron transport layer, an electron injection layer, and a cathode will be described. An anode is formed by forming a thin film of an anode material on an appropriate substrate by an evaporation method or the like, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A target organic EL element is obtained by co-evaporating a host material and a dopant material on the thin film to form a thin film as a light-emitting layer, forming an electron transport layer and an electron injection layer on the light-emitting layer, and further forming a thin film containing a substance for a cathode as a cathode by an evaporation method or the like. In the production of the organic EL element, the order of production may be reversed, and the organic EL element may be produced in the order of cathode, electron injection layer, electron transport layer, light-emitting layer, hole transport layer, hole injection layer, and anode.
When a dc voltage is applied to the organic EL element obtained as described above, the anode may be applied with a + polarity and the cathode may be applied with a-polarity, and when a voltage of about 2V to 40V is applied, light emission can be observed from the transparent or translucent electrode side (anode or cathode, or both). In addition, the organic EL element emits light even when a pulse current or an alternating current is applied thereto. In addition, the waveform of the applied alternating current may be arbitrary.
< 2-1-11. Application example of organic electroluminescent element
The organic EL element is also applicable to a display device, an illumination device, or the like.
A display device or an illumination device including an organic EL element can be manufactured by a known method such as connecting the organic EL element to a known driving device, and can be driven by a known driving method such as direct current driving, pulse driving, or alternating current driving.
Examples of the display device include: a panel display such as a color flat panel display, a flexible display such as a flexible color organic Electroluminescence (EL) display, and the like (for example, refer to japanese patent laid-open No. 10-335066, japanese patent laid-open No. 2003-321546, and japanese patent laid-open No. 2004-281086). The display mode of the display may be, for example, either a matrix or a segment mode. Furthermore, the matrix display and the segment display may coexist in the same panel.
In the matrix, pixels for display are two-dimensionally arranged in a lattice shape, a mosaic shape, or the like, and characters or images are displayed by a set of pixels. The shape or size of the pixel is determined according to the application. For example, in image and character display of a personal computer, a monitor, and a television, a rectangular pixel having a side of 300 μm or less is generally used, and in the case of a large-sized display such as a display screen, a pixel having a side of mm level is used. In the case of monochrome display, pixels of the same color may be arranged, and in the case of color display, pixels of red, green, and blue are arranged in parallel to perform display. In this case, a triangular shape and a striped shape are typical. Also, as a driving method of the matrix, any one of a line-sequential (line-sequential) driving method or an active matrix may be used. The line sequential driving has an advantage of a simple structure, but when the operating characteristics are taken into consideration, the active matrix may be more excellent, and therefore the driving method needs to be used separately depending on the application.
In the segmentation method (type), a pattern is formed so as to display information determined in advance, and the determined region is caused to emit light. Examples thereof include: time and temperature display in a digital clock or a thermometer, operation state display of an audio device or an induction cooker, panel display of an automobile, and the like.
Examples of the illumination device include an illumination device such as an indoor illumination, a backlight of a liquid crystal display device, and the like (see, for example, japanese patent laid-open nos. 2003-257621, 2003-277741, 2004-119211, and the like). Backlights are used mainly for improving visibility of display devices that do not emit light, and are used for liquid crystal display devices, clocks, audio devices, automobile panels, display panels, signs, and the like. In particular, as a backlight for personal computer applications in which thinning is becoming an issue in liquid crystal display devices, when it is considered that thinning is difficult in the conventional system including a fluorescent lamp or a light guide plate, a backlight using an organic EL element has characteristics of being thin and lightweight.
< 2-2. Other organic devices >
The polycyclic aromatic compound of the present invention can be used for the production of an organic field effect transistor, an organic thin film solar cell, or the like, in addition to the organic electroluminescent element.
An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and includes a gate electrode in addition to an active electrode and a drain electrode. The organic field effect transistor is a transistor as follows: when a voltage is applied to the gate electrode, an electric field is generated, and the flow of electrons (or holes) flowing between the source electrode and the drain electrode can be arbitrarily blocked to control the current. A field effect transistor is easy to be miniaturized compared with a single transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.
In general, the organic field effect transistor may be configured such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound of the present invention, and a gate electrode is provided through an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. Examples of the element structure include the following structures.
(1) Substrate/gate electrode/insulator layer/source and drain electrodes/organic semiconductor active layer
(2) Substrate, gate electrode, insulator layer, organic semiconductor active layer, source electrode and drain electrode
(3) Substrate/organic semiconductor active layer/source electrode and drain electrode/insulator layer/gate electrode
(4) Substrate/source electrode and drain electrode/organic semiconductor active layer/insulator layer/gate electrode
The organic field effect transistor configured as described above can be applied to a pixel driving switching element of an active matrix driving type liquid crystal display or an organic electroluminescence display, and the like.
An organic thin-film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are stacked on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The polycyclic aromatic compound of the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, or an electron transport layer, depending on the physical properties thereof. In an organic thin film solar cell, the polycyclic aromatic compound of the present invention can function as a hole transport material or an electron transport material. The organic thin-film solar cell may suitably include a hole blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like, in addition to the above. In the organic thin film solar cell, known materials used in the organic thin film solar cell can be appropriately selected and used in combination.
< 3. Wavelength converting Material
The polycyclic aromatic compound of the present invention is useful as a wavelength converting material.
The application of multicolor technology based on a color conversion method to a liquid crystal display or an organic EL display, illumination, and the like is being actively studied. The color conversion is to convert the emission wavelength from the light-emitting body into light having a longer wavelength, and means to convert ultraviolet light or blue light into green light or red light, for example. The wavelength conversion material having the color conversion function is formed into a film, and for example, is combined with a blue light source, whereby three primary colors of blue, green, and red, that is, white light can be extracted from the blue light source. A full color display (full color display) can be manufactured by using a white light source in which a blue light source and a wavelength conversion film having a color conversion function are combined as a light source unit, and combining the white light source with a liquid crystal driving section and a color filter. In addition, without a liquid crystal driving portion, the liquid crystal display device can be used as a white light source as it is, and can be applied to a white light source such as a light-emitting diode (LED) lighting. Further, a full-color organic EL display can be manufactured without using a metal mask by using a blue organic EL element as a light source and combining it with a wavelength conversion film that converts blue light into green light and red light. Further, a blue micro LED is used as a light source in combination with a wavelength conversion film that converts blue light into green light and red light, whereby a full-color micro LED display can be manufactured at low cost.
The polycyclic aromatic compound of the present invention is useful as the wavelength converting material. Ultraviolet light or light from a light source or a light-emitting element that generates blue light having a shorter wavelength can be converted into blue light or green light having high color purity and suitable for use in a display device (a display device or a liquid crystal display device using an organic EL element) using a wavelength conversion material containing the polycyclic aromatic compound of the present invention. The color to be converted can be adjusted by appropriately selecting the substituent of the polycyclic aromatic compound of the present invention, a binder resin used in the wavelength converting composition described later, and the like. The wavelength converting material is prepared as a wavelength converting composition containing the polycyclic aromatic compound of the present invention. In addition, a wavelength conversion film can also be formed using the wavelength conversion composition.
The wavelength conversion composition may further contain a binder resin, other additives, and a solvent in addition to the polycyclic aromatic compound of the present invention. As the binder resin, for example, resins described in paragraphs 0173 to 0176 of international publication No. 2016/190283 can be used. As other additives, compounds described in paragraphs 0177 to 0181 of International publication No. 2016/190283 can be used. As the solvent, reference is made to the description of the solvent contained in the composition for forming a light-emitting layer.
The wavelength conversion film includes a wavelength conversion layer formed by curing a wavelength conversion composition. As a method for producing a wavelength conversion layer from the wavelength conversion composition, a known film forming method can be referred to. The wavelength conversion film may contain only a wavelength conversion layer formed of the composition containing the polycyclic aromatic compound of the present invention, or may contain other wavelength conversion layers (for example, a wavelength conversion layer that converts blue light into green light or red light, or a wavelength conversion layer that converts blue light or green light into red light). Further, the wavelength conversion film may include a base material layer or a barrier layer for preventing the color conversion layer from being deteriorated by oxygen, moisture, or heat.
[ examples ]
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. Further, in the examples, me is methyl, et is ethyl, i pr is isopropyl and tBu is tert-butyl.
Synthesis example (1):
synthesis of Compound (1-1)
[ solution 117]
Figure BDA0003615335190001271
The intermediate (X-1) (47.0 g), 1-tert-butyl-3, 4, 5-trichlorobenzene (23.8 g), dichlorobis [ di-tert-butyl (4-dimethylaminophenyl) phosphino ] palladium (II) (Pd-132) (0.909 g) as a palladium catalyst, sodium tert-butoxide (NaOtBu, 14.4 g) and toluene (500 ml) were put in a flask under nitrogen atmosphere and heated at 120 ℃ for 5 hours. After completion of the reaction, water and ethyl acetate were added to the reaction mixture and stirred, and then the organic layer was separated and washed with water. Thereafter, the crude product obtained by concentrating the organic layer was purified by means of a silica gel short path column (eluent: heptane), whereby 50.2g of intermediate (X-2) was obtained.
[ chemical formula 118]
Figure BDA0003615335190001272
Intermediate (X-2) (33.5 g), intermediate (X-3) (18.6 g), pd-132 (0.719 g) as a palladium catalyst, naOtBu (7.21 g) and toluene (300 ml) were placed in a flask under nitrogen atmosphere, and heated at 120 ℃ for 3 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Thereafter, the crude product obtained by concentrating the organic layer was purified by means of a silica gel short path column (eluent: toluene/heptane =1/9 (volume ratio)), whereby 42.2g of an intermediate (X-4) was obtained.
[ solution 119]
Figure BDA0003615335190001281
Under nitrogen atmosphere at 0 deg.C, intermediate (X-4) (10.1 g) and tert-butyl benzene (t-butyl benzene) t Bu-benzene (benzene, 100 ml) in a flask was added 1.60M t-butyllithium pentane solution ((R)) t BuLi,12.5 ml). After the completion of the dropwise addition, the temperature was raised to 70 ℃ and the mixture was stirred for 0.5 hour, and then a component having a boiling point lower than that of t-butylbenzene was removed by distillation under reduced pressure. Boron tribromide (2.06 g) was added after cooling to-50 ℃ and the mixture was allowed to warm to room temperature and stirred for 0.5 hour. Then, N-diisopropylethylamine (EtN) was added after cooling to 0 ℃ again i Pr 2 1.29 g), stirring at room temperature until heat generation ceased, heating to 100 ℃ and stirring with heating for 1 hour. The reaction solution was cooled to room temperature, and an aqueous sodium acetate solution cooled by an ice bath was added thereto, followed by addition of ethyl acetate for liquid separation. The organic layer was concentrated and purified by a silica gel short-path column (eluent: chlorobenzene). The obtained crude product was recrystallized from toluene to obtain 6.90g of compound (1-1).
[ chemical formula 120]
Figure BDA0003615335190001282
Compound (1-1) as a target of M/z (M + H) =979.58 was confirmed by Mass Spectrometry (MS).
Synthesis example (2): synthesis of Compound (1-13)
Compound (1-13) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-13).
Compound (1-13) as the target of M/z (M + H) =1111.67 was confirmed by MS.
[ solution 121]
Figure BDA0003615335190001291
Synthesis example (3): synthesis of Compound (1-22)
Compound (1-22) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-22).
Compound (1-22) as a target of M/z (M + H) =1057.62 was confirmed by MS.
[ chemical formula 122]
Figure BDA0003615335190001292
Synthesis example (4): synthesis of Compound (1-27)
Compound (1-27) was obtained by following the same procedure as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-27).
Compound (1-27) as the target of M/z (M + H) =1202.71 was confirmed by MS.
[ 123]
Figure BDA0003615335190001301
Synthesis example (5): synthesis of Compound (1-38)
Compound (1-38) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-38).
Compound (1-38) as a target of M/z (M + H) =1033.62 was confirmed by MS.
[ chemical 124]
Figure BDA0003615335190001302
Synthesis example (6): synthesis of Compound (1-46)
Compound (1-46) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-46).
Compound (1-46) as the target of M/z (M + H) =1143.73 was confirmed by MS.
[ solution 125]
Figure BDA0003615335190001311
Synthesis example (7): synthesis of Compound (1-50)
Compound (1-50) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-50).
Compound (1-50) as the target of M/z (M + H) =1017.65 was confirmed by MS.
[ chemical 126]
Figure BDA0003615335190001312
Synthesis example (8): synthesis of Compound (1-77)
Compound (1-77) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-77).
Compound (1-77) as the target of M/z (M + H) =1000.71 was confirmed by MS.
[ solution 127]
Figure BDA0003615335190001313
Synthesis example (9): synthesis of Compound (1-88)
Compound (1-88) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-88).
Compound (1-88) was confirmed by MS as the target of M/z (M + H) = 1035.64.
[ solution 128]
Figure BDA0003615335190001321
Synthesis example (10): synthesis of Compound (1-105)
Compound (1-105) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-105).
Compound (1-105) as the target of M/z (M + H) =977.56 was confirmed by MS.
[ solution 129]
Figure BDA0003615335190001322
The structure of the compound obtained by Nuclear Magnetic Resonance (NMR) measurement was confirmed.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.92(s,9H),1.09(s,9H),1.10(s,9H),1.37(s,6H),1.41(s,6H),1.47(s,9H),1.77(s,4H),6.27(s,1H),6.48(s,1H),6.60(d,1H),6.69(d,1H),7.33-7.39(m,4H),7.41(dd,1H),7.47-7.48(m,1H),7.51(dd,1H),7.59(d,1H),7.63-7.65(m,3H),7.90-7.94(m,3H),8.06-8.08(m,1H),8.17(d,1H),8.74(d,1H).
Synthesis example (11): synthesis of Compound (1-111)
Compound (1-111) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-111).
Compound (1-111) as a target of M/z (M + H) =951.55 was confirmed by MS.
[ solution 130]
Figure BDA0003615335190001331
The structure of the compound obtained by NMR measurement was confirmed.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.91(s,9H),1.11(s,9H),1.19(s,9H),1.38(s,9H),1.47(s,9H),2.14(s,3H),2.44(s,3H),6.19-6.31(m,2H),6.70(s,1H),7.15-7.25(m,2H),7.33-7.40(m,5H),7.47(dd,1H),7.60(d,3H),7.67(d,2H),7.95(d,1H),8.06-8.08(m,1H),8.17(d,1H),8.76(d,1H).
Synthesis example (12): synthesis of Compound (1-122)
Compound (1-122) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-122).
Compound (1-122) as the target of M/z (M + H) =1027.57 was confirmed by MS.
[ solution 131]
Figure BDA0003615335190001332
The structure of the compound obtained by NMR measurement was confirmed.
1 H-NMR(500MHz,CDCl 3 )：δ＝0.92(s,9H),1.11(s,9H),1.20(s,9H),1.39(s,9H),1.47(s,9H),2.19(s,3H),2.49(s,3H),6.25(s,1H),6.28(s,1H),6.70(d,1H),7.32-7.52(m,10H),7.57-7.66(m,5H),7.71(d,2H),8.00(d,1H),8.05-8.09(m,1H),8.18(d,1H),8.77(d,1H).
Synthesis example (13): synthesis of Compound (1-132)
Compound (1-132) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-132).
Compound (1-132) as the target of M/z (M + H) =975.55 was confirmed by MS.
[ solution 132]
Figure BDA0003615335190001341
Synthesis example (14): synthesis of Compound (1-138)
Compound (1-138) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-138).
Compound (1-138) as a target of M/z (M + H) =1031.61 was confirmed by MS.
[ solution 133]
Figure BDA0003615335190001342
Synthesis example (15): synthesis of Compound (1-151)
Compound (1-151) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-151).
Compound (1-151) was confirmed by MS as the target of M/z (M + H) = 1220.67.
[ solution 134]
Figure BDA0003615335190001343
Synthesis example (16): synthesis of Compound (1-156)
Compound (1-156) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-156).
Compound (1-156) as a target of M/z (M + H) =1222.68 was confirmed by MS.
[ chemical 135]
Figure BDA0003615335190001351
Synthesis example (17): synthesis of Compound (1-166)
Compound (1-166) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-166).
Compound (1-166) as a target of M/z (M + H) =1162.59 was confirmed by MS.
[ solution 136]
Figure BDA0003615335190001352
Synthesis example (18): synthesis of Compound (1-176)
Compound (1-176) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-176).
Compound (1-176) as a target of M/z (M + H) =1192.64 was confirmed by MS.
[ solution 137]
Figure BDA0003615335190001353
Synthesis example (19): synthesis of Compounds (1-186)
Compound (1-186) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-186).
Compound (1-186) as a target of M/z (M + H) =1300.77 was confirmed by MS.
[ 138]
Figure BDA0003615335190001361
Synthesis example (20): synthesis of Compound (1-192)
Compound (1-192) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-192).
Compound (1-192) as a target of M/z (M + H) =1092.57 was confirmed by MS.
[ solution 139]
Figure BDA0003615335190001362
Synthesis example (21): synthesis of Compound (1-193)
Compound (1-193) was obtained by following the same procedure as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-193).
Compound (1-193) was confirmed by MS as a target of M/z (M + H) = 1260.75.
[ solution 140]
Figure BDA0003615335190001371
Synthesis example (22): synthesis of Compound (1-194)
Compound (1-194) was obtained by following the same procedures as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-194).
Compound (1-194) was confirmed by MS as a target of M/z (M + H) = 1307.92.
[ solution 141]
Figure BDA0003615335190001372
Synthesis example (23): synthesis of Compound (1-197)
Compound (1-197) was obtained by following the same procedure as in Synthesis example 1 except that Compound (X-4) was changed to Compound (X-4-197).
Compound (1-197) as a target of M/z (M + H) =1293.96 was confirmed by MS.
[ solution 142]
Figure BDA0003615335190001373
Synthesis example (24): synthesis of Compound (1-200)
Compound (1-200) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-200).
Compound (1-200) as the target of M/z (M + H) =1012.41 was confirmed by MS.
[ solution 143]
Figure BDA0003615335190001381
Synthesis example (25): synthesis of Compound (1-203)
Compound (1-203) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-203).
Compound (1-203) was confirmed by MS as the target compound of M/z (M + H) = 1080.48.
[ solution 144]
Figure BDA0003615335190001382
Synthesis example (26): synthesis of Compound (1-214)
Compound (1-214) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-214).
Compound (1-214) as a target of M/z (M + H) =1122.52 was confirmed by MS.
[ solution 145]
Figure BDA0003615335190001391
Synthesis example (27): synthesis of Compound (1-217)
Compound (1-217) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-217).
Compound (1-217) as a target of M/z (M + H) =1136.54 was confirmed by MS.
[ solution 146]
Figure BDA0003615335190001392
Synthesis example (28): synthesis of Compound (1-244)
Compound (1-244) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-244).
Compound (1-244) as the target of M/z (M + H) =1218.52 was confirmed by MS.
[ solution 147]
Figure BDA0003615335190001393
Synthesis example (29): synthesis of Compound (1-256)
Compound (1-256) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-256).
Compound (1-256) as the target of M/z (M + H) =1322.68 was confirmed by MS.
[ solution 148]
Figure BDA0003615335190001401
Synthesis example (30): synthesis of Compound (1-260)
Compound (1-260) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-260).
Compound (1-260) as a target of M/z (M + H) =1182.58 was confirmed by MS.
[ 149]
Figure BDA0003615335190001402
Synthesis example (31): synthesis of Compound (1-267)
Compound (1-267) was obtained by following the same procedure as in Synthesis example 1, except that compound (X-4) was changed to compound (X-4-267).
Compound (1-267) was confirmed by MS as the target of M/z (M + H) = 1236.62.
[ solution 150]
Figure BDA0003615335190001403
Synthesis example (32): synthesis of Compound (1-276)
Compound (1-276) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-276).
Compound (1-276) as a target of M/z (M + H) =1048.64 was confirmed by MS.
[ solution 151]
Figure BDA0003615335190001411
Synthesis example (33): synthesis of Compound (1-280)
Compound (1-280) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-280).
Compound (1-280) as the target of M/z (M + H) =977.56 was confirmed by MS.
[ 152]
Figure BDA0003615335190001412
Synthesis example (34): synthesis of Compound (1-281)
Compound (1-281) was obtained by following the same procedure as in Synthesis example 1, except that Compound (X-4) was changed to Compound (X-4-281).
Compound (1-281) as a target of M/z (M + H) =975.55 was confirmed by MS.
[ solution 153]
Figure BDA0003615335190001413
Other compounds of the present invention can be synthesized by appropriately changing the compounds as raw materials by the method according to the synthesis example.
Method for evaluating basic physical properties of compound
< preparation of sample >
When the absorption characteristics and the light emission characteristics (fluorescence and phosphorescence) of a compound to be evaluated are evaluated, there are a case where the compound to be evaluated is dissolved in a solvent and evaluated in the solvent, and a case where the compound to be evaluated is evaluated in a thin film state. Further, when the evaluation is performed in a thin film state, there are a case where only the compound to be evaluated is made thin and the evaluation is performed, and a case where the compound to be evaluated is dispersed in an appropriate matrix material and made thin and the evaluation is performed, depending on the use form of the compound to be evaluated in the organic EL element. Here, a thin film obtained by vapor deposition of only the compound to be evaluated is referred to as "single film", and a thin film obtained by applying and drying a coating liquid containing the compound to be evaluated and a matrix material is referred to as "coating film".
As the matrix material, commercially available polymethyl methacrylate (PMMA) or the like can be used. In this example, a sample was prepared by dissolving PMMA and a compound to be evaluated in toluene and then forming a thin film on a quartz transparent support substrate (10 mm × 10 mm) by a spin coating method.
In addition, a film sample in the case where the host compound is a matrix material was prepared in the following manner. A quartz transparent support substrate (10 mm. Times.10 mm. Times.1.0 mm) was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Changzhou industry Co., ltd.), a molybdenum vapor deposition boat containing a host compound and a molybdenum vapor deposition boat containing a dopant material were placed therein, and then a vacuum chamber was depressurized to 5X 10 -4 Pa. Next, the evaporation boat containing the host compound and the evaporation boat containing the dopant material were heated at the same time, and the host compound and the dopant material were co-evaporated to an appropriate film thickness to form a mixed thin film (sample) of the host compound and the dopant material. Here, the deposition rate is controlled according to a set mass ratio of the host compound to the dopant material.
< evaluation of absorption characteristics and luminescence characteristics >
The absorption spectrum of the sample was measured using an ultraviolet-visible near-infrared spectrophotometer (Shimadzu corporation, UV-2600). The fluorescence spectrum or phosphorescence spectrum of the sample was measured using a spectrofluorometer (Hitachi High-Tech (manufactured by Hitachi High-Tech Co., ltd., F-7000)).
For measurement of fluorescence spectrum, photoluminescence (photoluminescence) was measured by excitation at an appropriate excitation wavelength at room temperature. For the measurement of the phosphorescence spectrum, the measurement was performed in a state in which the sample was immersed in liquid nitrogen (temperature 77K) using an attached cooling unit. In order to observe the phosphorescence spectrum, the delay time from the irradiation of the excitation light until the start of measurement was adjusted using a light chopper (optical chopper). With respect to the sample, photoluminescence was measured by excitation at an appropriate excitation wavelength.
In addition, fluorescence quantum yield (PLQY) was measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics (Strand), C9920-02G).
Next, evaluation of basic properties of the polycyclic aromatic compound of the present invention will be described.
< evaluation of fluorescence lifetime (delayed fluorescence) >
The fluorescence lifetime was measured at 300K using a fluorescence lifetime measuring device (manufactured by Hamamatsu Photonics (Strand), C11367-01). Specifically, a light-emitting component having a fast fluorescence lifetime and a light-emitting component having a slow fluorescence lifetime are observed at maximum emission wavelengths measured at appropriate excitation wavelengths. In the measurement of the fluorescence lifetime of a general organic EL material emitting fluorescence at room temperature, the triplet component is deactivated by heat, and thus a slow light emitting component in which the triplet component derived from phosphorescence participates is hardly observed. In the case where a slow light-emitting component is observed in a compound to be evaluated, triplet energy indicating a long excitation lifetime is shifted to singlet energy by thermal activation, and is observed as delayed fluorescence.
< calculation of energy gap (Eg) >)
From the long wavelength end a (nm) of the absorption spectrum obtained by the method, it was calculated by Eg = 1240/a.
< measurement of ionization potential (Ip) >
A transparent supporting substrate (28 mm. Times.26 mm. Times.0.7 mm) on which ITO (indium tin oxide) was vapor-deposited was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by the Changzhou industry), a molybdenum vapor deposition boat containing a target compound was placed, and then the pressure in a vacuum chamber was reduced to 5X 10 -4 Pa. Next, the evaporation boat was heated to evaporate the target compound, thereby forming a single film (undoped) of the target compoundHetero (Neat) film).
The ionization potential of the target compound was measured using a photoelectron spectrometer (PYS-201, sumitomo heavy machinery industry ltd) using the obtained individual film as a sample.
< calculation of Electron affinity (Ea) >
The electron affinity can be estimated from the difference between the ionization potential measured by the method and the energy gap calculated by the method.
< measurement of lowest excited singlet level E (S, sh) and lowest excited triplet level E (T, sh) >
A fluorescence spectrum of an individual film of a target compound formed on a glass substrate was observed at 77K with a second absorption peak on the longer wavelength side of the absorption spectrum as excitation light, and the lowest excited singlet level E (S, sh) was obtained from a shoulder on the shorter wavelength side of the peak of the fluorescence spectrum. Further, a phosphorescence spectrum was observed at 77K with a second absorption peak on the longer wavelength side of the absorption spectrum as excitation light for an individual film of the target compound formed on the glass substrate, and the lowest excited triplet level E (T, sh) was obtained from a shoulder on the shorter wavelength side of the peak of the phosphorescence spectrum.
Production and evaluation of organic EL element
Next, the production and evaluation of an organic EL device using the polycyclic aromatic compound of the present invention will be described.
The compound of the invention has proper energy gap (Eg) and high lowest excited triplet energy (E) T ) And a small Δ EST, and therefore, application to a light-emitting layer and a charge-transporting layer, for example, is expected, and particularly application to a light-emitting layer is expected.
< construction of organic EL element >
An organic EL device is produced using the polycyclic aromatic compound of the present invention.
[ element constitution A ]
The material composition of each layer in the organic EL device of example 1 is shown in table 1 below.
[ Table 1]
Figure BDA0003615335190001431
Chemical structures of "HI", "HAT-CN", "HT-1", "HT-2", "BH", "ET-1", "ET-2", "Liq", and "comparative compound 1" described in International publication No. 2020/080872, and "comparative compound 2" described in International publication No. 2019/132028, and "comparative compound 3" described in International publication No. 2020-251049, and "comparative compound 4" described in International publication No. 2020-251049, and "comparative compound 5" described in International publication No. 2019-132028, and "comparative compound 6" described in International publication No. 2020-111830 in tables 1 and 2 are shown below.
[ chemical 154]
Figure BDA0003615335190001441
[ solution 155]
Figure BDA0003615335190001451
(example 1)
A glass substrate (manufactured by Opto Science) of 26mm by 28mm by 0.7mm, which was prepared by polishing ITO, which had been deposited to a thickness of 180nm by sputtering, to 150nm, was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa vacuum deposition (Strand)), and a molybdenum vapor deposition boat and an aluminum nitride vapor deposition boat were respectively charged with HI, HAT-CN, HT-1, HT-2, BH, the compounds (1-1), ET-1, and ET-2, and with Liq, liF, and aluminum.
The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10 -4 Pa, HI was heated to 40nm thick, HAT-CN was heated to 5nm thick, and HT-1 was heated to 45nm thickThe hole layer including four layers was formed by performing vapor deposition, and then, HT-2 was heated to a film thickness of 10 nm. Then, BH and the compound (1-1) were heated simultaneously and vapor-deposited so that the film thickness became 25nm to form a light-emitting layer. The deposition rate was adjusted so that the mass ratio of BH and the compound (1-1) became approximately 97 to 3. Further, ET-1 was heated to a film thickness of 5nm and vapor deposition was performed, and then ET-2 was simultaneously heated with Liq to a film thickness of 25nm and vapor deposition was performed, thereby forming an electron layer including two layers. The deposition rate was adjusted so that the mass ratio of ET-2 to Liq became approximately 50 to 50. The deposition rate of each layer is 0.01nm/sec to 1 nm/sec. Then, liF was heated to form a film thickness of 1nm, and evaporation was performed at an evaporation rate of 0.01nm/sec to 0.1 nm/sec, and then aluminum was heated to form a film thickness of 100nm, and a cathode was formed, thereby obtaining an organic EL element.
(examples 2 to 34, comparative examples 1 to 6)
Organic EL devices of examples 2 to 34 and comparative examples 1 to 6 were obtained in the same manner as in example 1 except that the respective materials described in table 2 were used instead of the compound (1-1).
< evaluation items and evaluation methods >
The evaluation items include a driving voltage (V), an emission wavelength (nm), a CIE chromaticity (x, y), an external quantum efficiency (%), a maximum wavelength (nm) and a half-value width (nm) of an emission spectrum, and the like. For example, 1000cd/m can be used as the evaluation items 2 Value when light is emitted.
The quantum efficiency of a light-emitting element includes an internal quantum efficiency and an external quantum efficiency, and the internal quantum efficiency indicates a ratio of external energy injected as electrons (or holes) into a light-emitting layer of the light-emitting element to be converted into photons. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light-emitting element, and since a part of the photons generated in the light-emitting layer is absorbed or continuously reflected by the inside of the light-emitting element and is not emitted to the outside of the light-emitting element, the external quantum efficiency is lower than the internal quantum efficiency.
The measurement method of the spectral emission luminance (emission spectrum) and the external quantum efficiency is as follows. The luminance of the applied element was 1000cd/m using a voltage/current generator R6144 manufactured by Edwardten test (Advantest) 2 The voltage of (3) causes the element to emit light. The spectral radiance in the visible light region was measured from the direction perpendicular to the light-emitting surface using a spectral radiance meter SR-3AR manufactured by Topycon (TOPCON). Assuming that the light-emitting surface is a perfect diffusion surface, the number obtained by dividing the measured spectral emission luminance value of each wavelength component by the wavelength energy and multiplying by pi is the number of photons at each wavelength. Then, the number of photons is integrated in the observed full wavelength region, and the total number of photons released from the element is set. The value obtained by dividing the applied current value by the elementary charge (elementary charge) is defined as the number of carriers injected into the device, and the value obtained by dividing the total number of photons released from the device by the number of carriers injected into the device is the external quantum efficiency. The half-value width of the emission spectrum is determined as the width between the upper and lower wavelengths at which the intensity becomes 50% with the maximum emission wavelength as the center.
In the organic EL devices of examples 1 to 34 and comparative examples 1 to 6, a DC voltage was applied to an ITO electrode as an anode and a LiF/aluminum electrode as a cathode, and the voltage was measured at 1000cd/m 2 Characteristics when light is emitted.
The results are shown in Table 2.
[ Table 2]
Figure BDA0003615335190001461
Figure BDA0003615335190001471
[ industrial applicability ]
The polycyclic aromatic compound of the present invention is useful as a material for an organic device, particularly a material for a light-emitting layer for forming a light-emitting layer of an organic electroluminescent element. By using the polycyclic aromatic compound of the present invention as a dopant for a light-emitting layer, an organic electroluminescent element which emits light at a low voltage and high efficiency can be obtained.

Claims (11)

1. A polycyclic aromatic compound having one or more structures containing a structural unit represented by the following formula (1);
Figure FDA0003615335180000011
in the formula (1), the reaction mixture is,
z is each independently N or C-R 11 Wherein Z = Z can be > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
R 11 each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl,
the two aryl groups of the diarylamino group are not bonded to each other or are bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group are not bonded to each other or are bonded via a linking group, the aryl group and the heteroaryl group of the arylheteroarylamino group are not bonded to each other or are bonded via a linking group, the two aryl groups of the diarylboron group are not bonded to each other or are bonded via a single bond or a linking group,
two adjacent R 11 Are bonded to each other to form an aryl or heteroaryl ring, or are not bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of the formed aryl and heteroaryl rings being independently of each other via R 11 Either substituted, or unsubstituted,
the ring C is a ring represented by the formula (C),
in the formula (C), X c Is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
Z C are each independently N or C-R C ，
R C Each independently of the other is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl radicals of the diarylamino radical being not bonded to one another or being bonded via a linking group, the two heteroaryl radicals of the diarylamino radical being not bonded to one another or being bonded via a linking group, the aryl radical of the arylheteroarylamino radical being bonded to one another or being bonded via a linking group, the two aryl radicals of the diarylboron radical being not bonded to one another or being bonded via a single bond or a linking groupSo as to bond the metal wire and the metal wire,
two adjacent R C Can be bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of said aryl and heteroaryl rings being independently of each other via R C Either substituted, or unsubstituted,
wherein any two consecutive Z C In which one is with Y 1 The bound carbon, another being with X 2 A bonded carbon;
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 One is > N-GA, the other is > N-GB,
GA is a monovalent group represented by the formula (GA);
in the formula (GA), the compound is represented by the formula (GA),
Z a are each independently N or C-R a ，
R a Each independently of the others being hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl groups of the diarylamino group not being bonded to each other or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group not being bonded to each other or being bonded via a linking group, the aryl group of the arylheteroarylamino group not being bonded to a heteroaryl group or being bonded via a linking group, the two aryl groups of the diarylboron group not being bonded to each other or being bonded via a single bond or a linking group,
two adjacent R a Can be mutually bondedJoined to form an aryl or heteroaryl ring, at least one hydrogen of which is substituted with R a Either substituted, or unsubstituted,
a is > O, > N-R, > Si (-R) 2 、＞C(-R) 2 R > N-R, said > Si (-R) 2 R of (b), and said > C (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > Si (-R) 2 Two R of (a) and said > C (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
wherein the monovalent group represented by the formula (GA) is bonded to X at any position 1 Or X 2 N-GA of > N-GA;
GB is a monovalent radical represented by the formula (GB),
in the formula (GB), the reaction mixture is,
Z b are each independently N or C-R b ，
R b Each independently of the others being hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboron, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, or substituted silyl, the two aryl groups of the diarylamino group not being bonded to each other or being bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group not being bonded to each other or being bonded via a linking group, the aryl group of the arylheteroarylamino group not being bonded to a heteroaryl group or being bonded via a linking group, the two aryl groups of the diarylboron group not being bonded to each other or being bonded via a single bond or a linking group,
two adjacent R b Can be combined with each otherAre bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of said aryl and heteroaryl rings formed being independently of each other via R b Either substituted, or unsubstituted,
wherein the monovalent group represented by the formula (GB) is bonded to X at any position 1 Or X 2 N-GB;
at least one of the structures selected from the group consisting of aryl and heteroaryl rings is condensed or not condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane being substituted, at least one-CH in the cycloalkane 2 -is substituted by-O-, or unsubstituted, and;
at least one hydrogen in the structure is substituted with cyano, halogen, or deuterium, or unsubstituted.
2. The polycyclic aromatic compound according to claim 1, wherein the structural unit represented by the formula (1) is represented by the formula (1 a), the formula (1 b), the formula (1 c), the formula (1 d), the formula (1 e), the formula (1 f), the formula (1 g) or the formula (1 h);
Figure FDA0003615335180000031
in the formula (1 a), the formula (1 b), the formula (1 c), the formula (1 d), the formula (1 e), the formula (1 f), the formula (1 g) and the formula (1 h),
z is each independently N or C-R 11 Wherein Z = Z may each independently be > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
R 11 each independently hydrogen, substituted or unsubstituted aromaticA group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted diarylamino group, a substituted or unsubstituted diheteroarylamino group, a substituted or unsubstituted arylheteroarylamino group, a substituted or unsubstituted diarylboron group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group, the two aryl groups of the diarylamino group being not bonded to each other or bonded via a linking group, the two heteroaryl groups of the diheteroarylamino group being not bonded to each other or bonded via a linking group, the aryl group and heteroaryl group of the arylheteroarylamino group being not bonded to each other or bonded via a linking group, the two aryl groups of the diarylboron group being not bonded to each other or bonded via a single bond or a linking group,
two adjacent R 11 Are bonded to each other to form an aryl or heteroaryl ring, or are not bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of the formed aryl and heteroaryl rings being independently of each other via R 11 Substituted, or unsubstituted;
X c is > O, > N-R, > C (-R) 2 、＞Si(-R) 2 S or Se, said > N-R, said > C (-R) 2 And said > Si (-R) 2 Each R of (A) is independently hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl, > C (-R) 2 And said > Si (-R) 2 Two R's are bonded to each other to form a ring, or are not bonded to each other to form a ring,
Z C are each independently N or C-R C ，R C Each independently is hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboronA group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted silyl group, two aryl groups of the diarylamino group being not bonded to each other or bonded via a linking group, two heteroaryl groups of the diheteroarylamino group being not bonded to each other or bonded via a linking group, an aryl group and a heteroaryl group of the arylheteroarylamino group being not bonded to each other or bonded via a linking group, two aryl groups of the diarylboron group being not bonded to each other or bonded via a single bond or a linking group,
two adjacent R C Can be bonded to each other to form an aryl or heteroaryl ring, at least one hydrogen of said aryl and heteroaryl rings formed being independently of each other via R C Substituted, or unsubstituted;
Y 1 is B, P = O, P = S, al, ga, as, si-R, or Ge-R, said Si-R and R of said Ge-R being a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;
X 1 and X 2 One is > N-GA, the other is > N-GB,
GA is a monovalent group represented by the formula (GA);
GB is a monovalent group represented by the formula (GB);
at least one of the structures selected from the group consisting of aryl and heteroaryl rings is condensed or not condensed with at least one cycloalkane, at least one hydrogen in the cycloalkane being substituted, at least one-CH in the cycloalkane 2 -is substituted by-O-, or unsubstituted, and;
at least one hydrogen in the structure is substituted with cyano, halogen, or deuterium, or unsubstituted.
3. The polycyclic aromatic compound according to claim 2, wherein the structural unit represented by formula (1) is represented by formula (1 a).
4. Polycyclic aromatic compound according to any one of claims 1 to 3, wherein Z are all C-R 11 。
5. The polycyclic aromatic compound according to any one of claims 1 to 4, wherein the monovalent group represented by formula (GA) is a group represented by formula (GA-1) or formula (GA-4) wherein X is a substituent or a group represented by formula (GA-1) or formula (GA-4) wherein either or both of hydrogen of the group represented by formula (GA) or formula (GA-4) wherein X is a substituent are substituted with an alkyl group or a cycloalkyl group, and
the monovalent group represented by the formula (GB) is a group represented by the formula (GB-1), the formula (GB-3), the formula (GB-6), the formula (GB-13) or the formula (GB-14) wherein R is a substituent, a group represented by the formula (GB-1), the formula (GB-3), the formula (GB-6), the formula (GB-13) or the formula (GB-14) wherein one or two hydrogens of the group represented by the substituent are substituted with an alkyl group or a cycloalkyl group, or a group represented by the formula (GB-1), the formula (GB-3), the formula (GB-6), the formula (GB-13) or the formula (GB-14) wherein R is a substituent wherein at least one of the benzene rings of the group represented by the formula (GB-1), the formula (GB-3), the formula (GB-6), the formula (GB-13) or the formula (GB-14) wherein R is a substituent is at least one condensed group,
Figure FDA0003615335180000051
6. the polycyclic aromatic compound according to claim 1, represented by any one of the following formulae;
Figure FDA0003615335180000052
Figure FDA0003615335180000061
Figure FDA0003615335180000071
Figure FDA0003615335180000081
in the formula, me is methyl, tBu is tert-butyl, and D is deuterium.
7. A material for organic devices, comprising the polycyclic aromatic compound according to any one of claims 1 to 6.
8. An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer disposed between the pair of electrodes, the light-emitting layer containing the polycyclic aromatic compound according to any one of claims 1 to 6.
9. The organic electroluminescent element according to claim 8, wherein the light-emitting layer comprises a host and the polycyclic aromatic compound as a dopant.
10. The organic electroluminescent element according to claim 9, wherein the host is an anthracene compound, a fluorene compound, or a dibenzo
Figure FDA0003615335180000091
A compound is provided.
11. A display device or a lighting device comprising the organic electroluminescent element according to any one of claims 8 to 10.
CN202210442993.2A 2021-04-26 2022-04-22 Polycyclic aromatic compound, material for organic device, organic electroluminescent element, display device, or lighting device Pending CN115246853A (en)

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